Nonvolatile memory device and method of manufacturing the same

ABSTRACT

To realize miniaturization and increased capacity of memories by lowering break voltage for causing resistance change and suppressing variation in break voltage. 
     The nonvolatile memory device ( 10 ) in the present invention includes: a lower electrode ( 105 ) formed above a substrate ( 100 ); a first variable resistance layer ( 106   a ) formed above the lower electrode ( 105 ) and comprising a transitional metal oxide; a second variable resistance layer ( 106   b ) formed above the first variable resistance layer ( 106   a ) and comprising a transitional metal oxide having higher oxygen content than the transitional metal oxide of the first variable resistance layer ( 106   a ); and an upper electrode ( 107 ) formed above the second variable resistance layer ( 106   b ), wherein a step ( 106   ax ) is formed in an interface between the first variable is resistance layer ( 106   a ) and the second variable resistance layer ( 106   b ). The second variable resistance layer ( 106   b ) is formed covering the step ( 106   ax ) and has a bend ( 106   bx ) above the step ( 106   ax ).

TECHNICAL FIELD

The present invention relates to a variable resistance nonvolatilememory device which has a resistance value that changes according toapplication of voltage pulse.

BACKGROUND ART

Recent years have seen increasing high performance in electronic devicessuch as mobile information devices and information appliances followingthe development of digital technology. With the increased highperformance in these electronic devices, miniaturization and increase inspeed of semiconductor elements used are rapidly advancing. Among these,application for large-capacity nonvolatile memories represented by aflash memory is rapidly expanding. In addition, as a next-generationnew-type nonvolatile memory to replace the flash memory, research anddevelopment on a variable resistance nonvolatile storage element whichuses what is called a variable resistance element is advancing. Here,variable resistance element refers to an element having a property inwhich a resistance value reversibly changes according to electricalsignals, and capable of storing information corresponding to theresistance value in a nonvolatile manner.

As an example of such variable resistance element, there is proposed anonvolatile memory device having a variable resistance layer in whichtransition metal oxides of different oxygen content are stacked. Forexample, Patent Literature 1 discloses selectively causing theoccurrence of oxidation/reduction reaction in an electrode interfacewhich is in contact with a variable resistance layer having high oxygencontent, to stabilize resistance change.

The aforementioned conventional variable resistance element includes alower electrode, a variable resistance layer, and an upper electrode,and a memory array is configured from a two-dimensional orthree-dimensional array of such variable resistance element. In each ofthe variable resistance elements, the variable resistance layer is of astacked structure including a first variable resistance layer and asecond variable resistance layer, and, in addition, the first and secondvariable resistance layers comprise the same type of transitional metaloxide. The oxygen content of the transitional metal oxide comprised inthe second variable resistance layer is higher than the oxygen contentof the transitional metal oxide comprised in the first variableresistance layer. By adopting such a structure, when voltage is appliedto the variable resistance element, most of the voltage is applied tothe second variable resistance layer which has higher oxygen content andexhibits a higher resistance value. Furthermore, oxygen, which cancontribute to the reaction, is abundant in the vicinity of theinterface. Therefore, oxidation/reduction reaction occurs selectively atthe interface between the upper electrode and the second variableresistance layer, and stable resistance change can be realized.

CITATION LIST Patent Literature

[PTL 1]

International Publication No. 2008/149484

SUMMARY OF INVENTION Technical Problem

However, in the above-described conventional variable resistancenonvolatile memory device, there is the problem that the break voltageto be initially applied to the variable resistance element in order totransition to a state in which resistance change is started is high, andthat the break voltage varies for each variable resistance elementincluded in the memory array.

The present invention is conceived to solve the aforementioned problemand has as an object to provide (i) a variable resistance nonvolatilememory device capable of reducing break voltage compared to theconventional device, and suppressing variation of break voltage amongrespective variable resistance elements, and (ii) a manufacturing methodthereof.

Solution to Problem

In order to achieve the aforementioned object, a first nonvolatilememory device according to an aspect of the present invention includes:a substrate; a lower electrode formed above the substrate; a firstvariable resistance layer formed above the lower electrode andcomprising a first transitional metal oxide; a second variableresistance layer formed above the first variable resistance layer andcomprising a second transitional metal oxide having an oxygen contentthat is higher than an oxygen content of the first transitional metaloxide; and an upper electrode formed above the second variableresistance layer, wherein a step is formed in an interface between thefirst variable resistance layer and the second variable resistancelayer, and the second variable resistance layer is formed covering thestep and has a bend above the step. Here, the bend refers to a part atwhich the second variable resistance layer bends in the stackingdirection due to the influence of an abrupt step formed in the base, anddoes not include a bend caused by a gradually-changing, gentle stepshape. By adopting the above-described configuration, the shape of thestep of the first variable resistance layer is reflected, therebyforming the bend in the second variable resistance layer on the step,and thus it is possible, through electric field concentration, to causethe break phenomenon even with a low voltage, with the bend as astarting point of the initial break. Furthermore, since the shape of thestep can be formed with intentional control, the shape of the bend ofthe second variable resistance layer becomes stable, and thus variationin break voltage does not increase. Therefore, lowering the breakvoltage and suppressing variation therein can both be achieved, andminiaturization and increased capacity of memories can be realized.

Furthermore, it is preferable that the first nonvolatile memory deviceinclude a contact plug below the lower electrode, and that an interfacebetween the lower electrode and the first variable resistance layer beflat. By adopting such a configuration, even though a recess is createdabove the contact plug, the lower electrode above such recess is thick,and thus the surface of the electrode can be made flat. The shape andfilm thickness of the second variable resistance layer at the bend isdependent only on the shape of the step of the first variable resistancelayer, and is not affected by the shape of the base in a further lowerlayer. Thus, it is possible to reduce variation in resistance changecharacteristics between each bit caused by the base.

In order to achieve the aforementioned object, a second nonvolatilememory device according to an aspect of the present invention includes:a substrate; a lower electrode formed above the substrate; a secondvariable resistance layer formed above the lower electrode andcomprising a second transitional metal oxide; a first variableresistance layer formed above the second variable resistance layer andcomprising a first transitional metal oxide having an oxygen contentthat is lower than an oxygen content of the second transitional metaloxide; and an upper electrode formed above the first variable resistancelayer, wherein a step is formed in an interface between the lowerelectrode and the second variable resistance layer, and the secondvariable resistance layer is formed covering the step and has a bendabove the step. By adopting such a configuration, the shape of the stepof the lower electrode is reflected, thereby forming the bend in thesecond variable resistance layer on the step, and thus it is possible,through electric field concentration, to cause the break phenomenon evenwith a low voltage, with the bend as a starting point of the initialbreak. Furthermore, since the shape of the step can be formed withintentional control, the shape of the bend of the second variableresistance layer becomes stable, and thus variation in break voltagedoes not increase. Therefore, lowering the break voltage and suppressingvariation therein can both be achieved, and miniaturization andincreased capacity of memories can be realized.

In the first and second nonvolatile memory devices described above, thebend of the second variable resistance layer is straight-shaped when thesecond variable resistance layer is seen from above. By adopting such aconfiguration, straight step patterns can be formed in the firstvariable resistance layers or lower electrodes across a plurality ofadjacent variable resistance elements, in the same pattern, and thusminiaturization does not pose a problem in the forming of the straightstep pattern. Therefore, since a low-cost mask can be used,manufacturing cost reduction becomes possible, and the manufacturingmethod for forming the straight step patter is simplified.

Furthermore, in the first and second nonvolatile memory devicesdescribed above, the bend of the second variable resistance layer may bering-shaped when the second variable resistance layer is seen fromabove. By adopting such a configuration, a longer step pattern can beformed in a single variable resistance element than with the straightstep pattern. As such, the length of the bend of the second variableresistance layer can be extended, and due to the increase in the regionserving as a starting point of the break phenomenon, further lowering ofthe break voltage becomes possible. Furthermore, depending on the case,it is possible to share with a mask for forming contact holes above andbelow the variable resistance element, and thus reduction ofmanufacturing cost becomes possible.

Furthermore, in the first and second nonvolatile memory devicesdescribed above, the step of the first variable resistance layer mayinclude plural steps, and there may be a crossing point at which theplural steps cross each other. By adopting such a configuration, thestep is biggest at the crossing point at which the steps cross, and thebend becomes bigger in the second variable resistance layer formed onthe step, and thus the second variable resistance layer tends to be alocally thin-film. Therefore, the electric field is easily concentratedat the crossing point, and thus allowing the location of the breakphenomenon to be fixed. Therefore, by placing the crossing point at thecentral part of the variable resistance element and away from the edgesof the variable resistance element, a filament can be formed at a partthat is minimally affected by etching damage and an oxidized region of alayer insulating film and the like. Therefore, variation in resistancechange characteristics is greatly reduced, and thus it is possible torealize a nonvolatile memory device having little bit variation andexcellent manufacturing yield.

In the first and second nonvolatile memory devices described above, thefirst variable resistance layer and the second variable resistance layermay each comprise an oxide layer of tantalum, hafnium, or zirconium.These materials have excellent retention characteristics for variableresistance elements and are materials that allow high-speed operation,and thus the advantageous effects of the present invention allow breakcharacteristics to be made extremely stable even for a variableresistance layer material that requires an initial break at the start ofresistance change.

In the first and second nonvolatile memory devices described above, adiode element may be formed in contact with the lower electrode or theupper electrode of the variable resistance element. In a memory cellstructure in which the variable resistance element and the diode elementare connected in series, it is necessary to add a voltage portion to bedistributed to the diode element and raise the voltage to be applied tothe memory cell, and thus the demand for lowering the voltage becomesgreater. In the nonvolatile memory device in the present embodiment, thebreak voltage of the variable resistance element can be lowered, andthus the voltage applied to the memory cell can be lowered. Furthermore,since the break phenomenon of the variable resistance element occurslocally, transient current flowing at the time of the break can bereduced. With this, destruction of the diode element can also beprevented.

The first method of manufacturing a nonvolatile memory device accordingto an aspect of the present invention includes: forming a lowerelectrode above a substrate; forming a first variable resistance layerabove the lower electrode, the first variable resistance layercomprising a first transitional metal oxide; forming a step in a surfaceof the first variable resistance layer; forming a second variableresistance layer to cover the step of the first variable resistancelayer and have a bend above the step, the second variable resistancelayer comprising a second transitional metal oxide having an oxygencontent that is higher than an oxygen content of the first transitionalmetal oxide; and forming an upper electrode above the second variableresistance layer.

Furthermore, the second method of manufacturing a nonvolatile memorydevice according to an aspect of the present invention includes: forminga lower electrode above a substrate; forming a step in a surface of thelower electrode; forming a second variable resistance layer to cover thestep of the lower electrode and have a bend above the step, the secondvariable resistance layer comprising a second transitional metal oxide;forming a first variable resistance layer above the second variableresistance layer, the first variable resistance layer comprising a firsttransitional metal oxide having an oxygen content that is lower than anoxygen content of the second transitional metal oxide; and forming anupper electrode above the first variable resistance layer.

By adopting such a manufacturing method, it is possible to reflect theshape of the step of the base and stably form the bend in the secondvariable resistance layer on the step, and thus it is possible, throughelectric field concentration, to cause the break phenomenon even with alow voltage, with the bend as a starting point of the initial break.Furthermore, since the shape of the step can be formed with intentionalcontrol, the shape of the bend of the second variable resistance layerbecomes stable, and thus variation in break voltage does not increase.Therefore, lowering the break voltage and suppressing variation thereincan both be achieved, and miniaturization and increased capacity ofmemories can be realized.

Furthermore, the third method of manufacturing a first nonvolatilememory device according to an aspect of the present invention includes:forming a lower electrode above a substrate; forming a first variableresistance layer above the lower electrode, the first variableresistance layer comprising a first transitional metal oxide; forming asecond variable resistance layer above the first variable resistancelayer, the second variable resistance layer comprising a secondtransitional metal oxide having an oxygen content that is higher than anoxygen content of the first transitional metal oxide; additionallystacking the second variable resistance layer after forming a step inthe second variable resistance layer, so as to cover the step; andforming an upper electrode above the additionally-stacked secondvariable resistance layer.

By adopting such a manufacturing method, a thin-film region whereelectric fields easily concentrate can be formed in the second variableresistance layer, and thus it is possible to cause the break phenomenoneven with a low voltage, with the thin-film region as a starting pointof the initial break. Furthermore, since the shape of the step can beformed with intentional control, variation in the film thickness of thesecond variable resistance layer can be stabilized, and thus variationin break voltage does not increase. Therefore, lowering the breakvoltage and suppressing variation therein can both be achieved, andminiaturization and increased capacity of memories can be realized.

Advantageous Effects of Invention

The nonvolatile memory device in the present invention lowers breakvoltage and reduces variation in break voltage by intentionally forminga step in the surface of a base layer of the second variable resistancelayer and thereby stably forming a locally thin-filmed or bent part inthe second variable resistance layer on the step. By being able to lowerthe break voltage and ameliorate the variation in bit-units, the presentinvention can contribute significantly to miniaturization and increasedcapacity of memories.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1( a) is a cross-sectional view showing an example configuration ofa nonvolatile memory device in Embodiment 1 of the present invention,and FIG. 1( b) is a plan view of a first variable resistance layerincluded in the nonvolatile memory device.

FIG. 2( a) to (k) are cross-sectional views showing a method ofmanufacturing main parts of the nonvolatile memory device in Embodiment1 of the present invention.

FIGS. 3( a) and (b) are cross-sectional views showing a method ofmanufacturing main parts of the nonvolatile memory device in Embodiment1 of the present invention.

FIG. 4( a) to (e) are plan views showing a method of manufacturing mainparts of the nonvolatile memory device in Embodiment 1 of the presentinvention.

FIG. 5( a) is a cross-sectional view showing an example configuration ofa nonvolatile memory device in Embodiment 2 of the present invention,and FIG. 5( b) is a plan view of a first variable resistance layerincluded in the nonvolatile memory device.

FIG. 6( a) to (f) are cross-sectional views showing a method ofmanufacturing main parts of the nonvolatile memory device in Embodiment2 of the present invention.

FIG. 7( a) to (e) are plan views showing a method of manufacturing mainparts of the nonvolatile memory device in Embodiment 2 of the presentinvention.

FIG. 8A is a SEM image cross-sectional view of a main part in a processin which a step is formed in the first variable resistance layer, in themethod of manufacturing the nonvolatile memory device in Embodiment 2 ofthe present invention.

FIG. 8B is a graph showing break voltage characteristics of thenonvolatile memory device in Embodiment 2 of the present invention.

FIG. 9( a) is a cross-sectional view showing an example configuration ofa nonvolatile memory device in Embodiment 3 of the present invention,and FIG. 9( b) is a plan view of a lower electrode included in thenonvolatile memory device.

FIG. 10( a) to (g) are cross-sectional views showing a method ofmanufacturing main parts of the nonvolatile memory device in Embodiment3 of the present invention.

FIG. 11( a) to (f) are plan views showing a method of manufacturing mainparts of the nonvolatile memory device in Embodiment 3 of the presentinvention.

FIG. 12( a) is a cross-sectional view showing an example configurationof a nonvolatile memory device in Embodiment 4 of the present invention,and FIG. 12( b) is a plan view of a lower electrode included in thenonvolatile memory device.

FIG. 13( a) to (g) are cross-sectional views showing a method ofmanufacturing main parts of the nonvolatile memory device in Embodiment4 of the present invention.

FIG. 14( a) to (f) are plan views showing a method of manufacturing mainparts of the nonvolatile memory device in Embodiment 4 of the presentinvention.

FIG. 15 is a SEM image cross-sectional view of a main part in a processin which a step is formed in the lower electrode, in the method ofmanufacturing the nonvolatile memory device in Embodiment 4 of thepresent invention.

FIG. 16( a) is a cross-sectional view showing an example configurationof a nonvolatile memory device in Embodiment 5 of the present invention,FIG. 16( b) is a plan view of a first variable resistance layer includedin the nonvolatile memory device, and FIG. 16( c) is a perspective viewof the first variable resistance layer included in the nonvolatilememory device.

FIG. 17( a) to (g) are cross-sectional views showing a method ofmanufacturing main parts of the nonvolatile memory device in Embodiment5 of the present invention.

FIG. 18( a) to (c) are perspective views showing a method ofmanufacturing main parts of the nonvolatile memory device in Embodiment5 of the present invention.

FIG. 19( a) is a cross-sectional view showing an example configurationof a nonvolatile memory device in Embodiment 6 of the present invention,and FIG. 19( b) is a plan view of a first variable resistance layerincluded in the nonvolatile memory device.

FIG. 20( a) to (g) are cross-sectional views showing a method ofmanufacturing main parts of the nonvolatile memory device in Embodiment6 of the present invention.

FIG. 21( a) is a cross-sectional view showing an example configurationof a nonvolatile memory device in Embodiment 7 of the present invention,and FIG. 21( b) is a plan view of a first variable resistance layerincluded in the nonvolatile memory device.

FIG. 22( a) to (i) are cross-sectional views showing a method ofmanufacturing main parts of the nonvolatile memory device in Embodiment7 of the present invention.

FIG. 23( a) is a cross-sectional view showing an example configurationof a nonvolatile memory device in a modification of Embodiment 7 of thepresent invention, and FIG. 23( b) is a plan view of a first variableresistance layer included in the nonvolatile memory device.

FIG. 24 is a cross-sectional view showing an example configuration of anonvolatile memory device in a first comparative example.

FIG. 25 is a cross-sectional view showing an example configuration of anonvolatile memory device in a second comparative example.

FIG. 26A is a SEM image cross-sectional view of the nonvolatile memorydevice in the first comparative example.

FIG. 26B is a SEM image cross-sectional view of the nonvolatile memorydevice in the second comparative example.

FIG. 27 is a graph showing break voltage characteristics of thenonvolatile memory devices in the first and second comparative examples.

DESCRIPTION OF EMBODIMENTS

Hereinafter, results of experiments by the inventors showing variationin break voltages and the cause thereof shall be described prior todescribing the details of the present invention.

FIG. 24 shows, as a first comparative example, a variable resistancenonvolatile memory device 50 provided with a variable resistanceelement. As shown in FIG. 24, a first line 101 is formed on a substrate100, and a first interlayer insulating layer 102 is formed covering thefirst line 101. A first contact hole 103 is formed penetrating throughthe first interlayer insulating layer 102 and reaching the first line101, and a first contact plug 104 is formed filling the first contacthole 103. A variable resistance element including a lower electrode 105,a variable resistance layer 106, and an upper electrode 107 is formed onthe first interlayer insulating layer 102 and covering the first contactplug 104. A second interlayer insulating layer 108 is formed coveringthe variable resistance element, and a second contact plug 110 is formedfilling the a second contact hole 109 which penetrates through thesecond interlayer insulating layer 108, to connect the upper electrode107 and a second line 111. The variable resistance layer 106 isconfigured of the stacked structure of a first variable resistance layer106 a and a second variable resistance layer 106 b. The first variableresistance layer 106 a and the second variable resistance layer 106 bcomprise the same type of transitional metal oxide, and the oxygencontent of the transitional metal oxide forming the second variableresistance layer 106 b is higher than the oxygen content of thetransitional metal oxide forming the first variable resistance layer 106a.

By adopting such a structure, when voltage is applied to the variableresistance element, most of the voltage is applied to the secondvariable resistance layer 106 b which has higher oxygen content andexhibits a higher resistance value. Furthermore, oxygen which cancontribute to reaction is abundant in the vicinity of the interfacebetween the upper electrode 107 and the second variable resistance layer106 b. Therefore, oxidation/reduction reaction occurs selectively at theinterface between the upper electrode 107 and the second variableresistance layer 106 b, and stable resistance change can be realized.

Furthermore, FIG. 25 shows, as a second comparative example, a variableresistance nonvolatile memory device 60 provided with a variableresistance element. As shown in FIG. 25, the difference between thenonvolatile memory device 50 in FIG. 24 and the nonvolatile memorydevice 60 is that the surface of the lower electrode 105 is planarized.The top plane of the first contact plug 104 and the top plane of thefirst interlayer insulating layer 102 are not continuous and, although arecess (5 to 50 nm) is created in the non-continuous part, the lowerelectrode 105 is also formed in the part of the recess created above thefirst contact plug 104 inside the first contact hole 103, and thesurface of the lower electrode 105 is flat. In this manner, since thelower electrode 105 is also found inside the recess part created abovethe first contact plug 104, the thickness of the lower electrode 105above the recess becomes thicker than the thickness above the firstinterlayer insulating layer 102 as a result. According to thisstructure, since satisfactory flatness can be achieved for the surfaceof the lower electrode 105, it is possible to suppress variations in theshape and film thickness of the variable resistance layer 106 formed onthe lower electrode 105, and reduce variation in resistance changecharacteristics. Most of all, since the variation in film thickness ofthe second variable resistance layer 106 b, which has a thin filmthickness, high oxygen content, and high resistance, is suppressed andthe initial break operation for causing a resistance change (operationof locally short-circuiting a part of the second variable resistancelayer 106 b, and causing a transition to the state where resistancechange is to be started) becomes stable, it is possible to significantlyreduce variation among respective bits and realize a large-capacitynonvolatile memory.

FIG. 26A and FIG. 26B show specific configuration examples correspondingto the structures in FIG. 24 and FIG. 25, respectively. FIG. 26A is aSEM photograph cross-sectional view of an actually test-manufacturedvariable resistance element of the nonvolatile memory device 50 which isthe first comparative example described above, and FIG. 26B is a SEMphotograph cross-sectional view of an actually test-manufacturedvariable resistance element of the nonvolatile memory device 60 which isthe second comparative example. In both trial products, the firstcontact plug 104 is made of tungsten (W), and the lower electrode 105 isconfigured of a stacked structure of, from the top plane, tantalumnitride (TaN), titanium aluminum nitride (TiAlN), and titanium nitride(TiN). Furthermore, the variable resistance layer 106 comprises atantalum oxide, the first variable resistance layer 106 a having anoxygen content that is relatively closer to the stoichiometriccomposition comprises oxygen-deficient TaO_(x) (0<x<2.5), and the secondvariable resistance layer 106 b having an oxygen content that isrelatively high with respect to the first variable resistance layer 106a comprises an oxide having a composition that is close to Ta₂O₅. Theupper electrode 107 comprises iridium (Ir), and the second contact plug110 comprises tungsten (W). As shown in FIG. 26A, in the nonvolatilememory device 50, a recess is created on the first contact plug 104,which affects the shape of the lower electrode 105, and thus adepression of approximately 40 nm is created in the surface of the lowerelectrode 105. Therefore, the variable resistance layer 106 formed abovethe depression is sunken at the central part, and is slightly thinner atthe central part. In particular, since the second variable resistancelayer 106 b, to which voltage is effectively applied when voltage isapplied to the element, is thin at only a few nm, variations in theshape and film thickness thereof affect the variation in resistancechange characteristics. On the other hand, as shown in FIG. 26B, sincethe nonvolatile memory device 60 is formed such that the surface of thelower electrode 105 is flat, both the first variable resistance layer106 a and second variable resistance layer 106 b formed above the lowerelectrode 105 have a flat shape and there is very little variation infilm thickness.

FIG. 27 is a graph (error bars show largest value and smallest value)showing the initial break voltages of the above described nonvolatilememory devices 50 and 60. “Initial break” refers to the localizedshort-circuiting of a part of the second variable resistance layer 106 bhaving a higher oxygen content and exhibiting a higher resistance valueto cause transition to a state where resistance change can start, whenvoltage is initially applied to the variable resistance elementimmediately after manufacturing (also the same hereafter). The graphevaluates the initial break voltage required when the variableresistance element and a load resistance of 5 kΩ are connected inseries. In the nonvolatile memory device 50, significant variation of 2to 6 V (average value of 5 V) can be seen in the break voltage. Thissuggests a variation in the direction of the thinning of the filmthickness or the localized short-circuiting of the second variableresistance layer 106 b due to the creation of the recess and thevariation in the recess amount (0 to 50 nm). On the other hand, in thenonvolatile memory device 60, variation in break voltage is suppressedbut the absolute value thereof is high at more or less 6 V. Here, it isconsidered that variation in break voltage is suppressed by the adoptionof the structure in which variation in the film thickness of the secondvariable resistance layer 106 b is not easily affected even when theamount of recess varies. However, on the other hand, it is consideredthat the break voltage becomes high since the presence of a locallythinned-out part and a bent part in the second variable resistance layer106 b have been eliminated, that is, the location in which breaking cantake place easily is eliminated.

The present invention solves the above-described problem and lowers theinitial break voltage and variations therein by stably forming a locallythin or bent part in the second variable resistance layer byintentionally forming a step in the surface of the first variableresistance layer or the lower electrode which serve as a base of thesecond variable resistance layer which determines the initial breakcharacteristics. In particular, being able to lower initial breakvoltage and ameliorate variation between bits can contributesignificantly to miniaturization and increased capacity of memories. Inother words, the present invention can provide a variable resistancenonvolatile memory device suited for increased capacity and a method ofmanufacturing the same.

Hereinafter, embodiments of the present invention shall be describedwith reference to the Drawings.

Embodiment 1

[Device Configuration]

FIG. 1( a) is a cross-sectional view of a nonvolatile memory device 10in Embodiment 1 of the present invention, and FIG. 1( b) is a plan viewof the first variable resistance layer 106 a included therein. It shouldbe noted that, hereinafter, a cross-sectional view refers to a diagramof the inside of a plane including a line parallel to the stackingdirection of a variable resistance element, and a plan view refers to aview seen from the stacking direction of the variable resistanceelement.

As shown in FIGS. 1( a) and (b), the nonvolatile memory device 10 inEmbodiment 1 includes: the substrate 100 which is a semiconductorsubstrate, and the like, on which the first line 101 is formed; thefirst interlayer insulating layer 102 comprising a silicon oxide film(film thickness: 500 to 100 nm) formed on the substrate 100 and coveringthe first line 101; and the first contact plug 104 having tungsten (W)as a primary component, formed by being filled into the first contacthole 103 (diameter: 50 to 300 nm) which penetrates through the firstinterlayer insulating layer 102 and reaches the first line 101. The topplane of the first contact plug 104 and the top plane of the firstinterlayer insulating layer 102 are not continuous (that is, not on thesame plane), and a recess (depth: 5 to 50 nm) is created in thenon-continuous part. In addition, a variable resistance element (500 nmsquare size), which includes: the lower electrode 105 (film thickness: 5to 100 nm) comprising tantalum nitride (TaN); the variable resistancelayer 106 (film thickness: 20 to 100 nm); and the upper electrode 107(film thickness: 5 to 100 nm) comprising a noble metal (platinum (Pt),iridium (Ir), palladium (pd), and the like), is formed on the firstinterlayer insulating layer 102 and covering the first contact plug 104.The second interlayer insulating layer 108 comprising a silicon oxidefilm (SiO, film thickness: 500 to 1000 nm) is formed covering thevariable resistance element, the second contact hole 109 (diameter: 50to 300 nm) is formed penetrating through the second interlayerinsulating layer 108 and reaching the upper electrode 107, and thesecond contact plug 110 having tungsten (W) as a primary component isformed inside the second contact hole 109. The second line 111 is formedon the second interlayer insulating layer 108 and covering the secondcontact plug 110. It should be noted that the step created on the firstcontact plug 104 is not transferred onto the surface of the lowerelectrode 105, and thus the lower electrode 105 is extremely flatthroughout the entire surface, and a continuous plane (flat plane) ismaintained. Therefore, although the nonvolatile memory device 10includes the first contact plug 104 below the lower electrode 105, theinterface between the lower electrode 105 and the first variableresistance layer 106 a is flat.

Here, the variable resistance layer 106 is configured of the stackedstructure of the first variable resistance layer 106 a (film thickness:18 to 95 nm) and the second variable resistance layer 106 b (filmthickness: 2 to 10 nm). The first variable resistance layer 106 acomprises a first transitional metal oxide which is a transitional metaloxide having, for example, an oxygen-deficient tantalum oxide (TaO_(x),0<x<2.5) as a primary component. The oxygen content of a secondtransitional metal oxide forming the second variable resistance layer106 b is higher than the oxygen content of the first transitional metaloxide forming the first variable resistance layer 106 a. Stateddifferently, the oxygen composition ratio of the second transitionalmetal oxide is higher than the oxygen composition ratio of the firsttransitional metal oxide. For example, assuming that the second variableresistance layer 106 b comprises a tantalum oxide (TaO_(y)), then x<y.When the first variable resistance layer 106 a and the second variableresistance layer 106 b comprise a transitional metal oxide other thantantalum, the first variable resistance layer 106 a and the secondvariable resistance layer 106 b comprise a material having a less degreeof oxygen deficiency from the stoichiometric composition exhibitinginsulating properties. It is possible to configure a variable resistancefilm of the same stacked structure even when an oxide such as hafnium(Hf) or zirconium (Zr) is used as another material comprised in thevariable resistance layer 106.

It should be noted that an oxygen-deficient transitional metal oxiderefers to an oxide having less oxygen content (atom number ratio:percentage of total number of atoms occupied by oxygen atoms) comparedto an oxide including a stoichiometric composition. When thetransitional metal is Ta, the composition of a stoichiometric oxide isTa₂O₅, and the proportion of the number of atoms of Ta and O is 2.5.Therefore, in an oxygen-deficient Ta oxide, the atom proportion of Taand O is greater than 0 and less than 2.5.

A straight step 106 ax (height: 1 to 30 nm, length 500 nm) such as thatshown in FIG. 1( b) is formed in the surface (the interface with thesecond variable resistance layer 106 b) of the first variable resistancelayer 106 a, and the second variable resistance layer 106 b is formedabove, covering the step 106 ax. A straight bend 106 bx of the secondvariable resistance layer 106 b is created above the step 106 ax of thesecond variable resistance layer 106 b.

The step 106 ax is positioned between the first contact plug 104 and thesecond contact plug 110 (the first contact hole 103 and the secondcontact hole 109), and is a part which causes a change in elevation inthe interface between the first variable resistance layer 106 a and thesecond variable resistance layer 106 b. The step 106 ax is configured ofa side plane that connects a first principal plane and a secondprincipal plane lower than the first principal plane which serve as aboundary planes between the first variable resistance layer 106 a andthe second variable resistance layer 106 b. This side plane is formed tohave, for example, a 90 degree angle with respect to one or both of thefirst principal plane and the second principal plane.

The step 106 ax is the part which includes an inflection point at whichthe flatness changes abruptly in the interface between the firstvariable resistance layer 106 a and the second variable resistance layer106 b, that is, a point at which the continuity of the flatness isinterrupted. When the first variable resistance layer 106 a and thesecond variable resistance layer 106 b are seen from above or below(when seen from the side in which the upper electrode 107 or the lowerelectrode 105 is provided), the step 106 ax is arranged straightly. Itis preferable that the step 106 ax be formed at the approximate centerin the radial direction of the first contact hole 103 and the secondcontact hole 109.

The bend 106 bx is positioned between the first contact plug 104 and thesecond contact plug 110 (the first contact hole 103 and the secondcontact hole 109), and is a part of the second variable resistance layer106 b which bends in the stacking direction of the first variableresistance layer 106 a and the second variable resistance layer 106 b inthe cross-sectional view. The bend 106 bx is provided along the step 106ax, and configured of a part above the side plane of the step 106 ax.

According to this configuration, the bend 106 bx of the second variableresistance layer 106 b is formed above the step 106 ax of the firstvariable resistance layer 106 a, and thus it is possible to cause theinitial break phenomenon even with a low voltage, with the bend 106 bxas a starting point of the initial break. Furthermore, since the stepshape of the first variable resistance layer 106 a is formed in anintentional and controlled manner, the shape of the bend 106 bx of thesecond variable resistance layer 106 b is stable, and thus variation inbreak voltage does not increase. Although only one straight step 106 axis formed here, a plurality of steps may be formed. Forming a pluralityis effective in terms of allowing the region serving as the startingpoint of initial break to be enlarged. With this, lowering the initialbreak voltage and suppressing variation therein can both be achieved,and miniaturization and increased capacity of memories can be realized.

Furthermore, the lower electrode 105 is also formed in the part of therecess created above the first contact plug 104 inside the first contacthole 103, and is formed so that the surface of the lower electrode 105is flat. Therefore, the shape and film thickness of the second variableresistance layer 106 b at the bend 106 bx is dependent only on the shapeof the step 106 ax of the first variable resistance layer 106 a, and isnot affected by the shape of the base of a lower layer to the firstvariable resistance layer 106 a. Thus, it is possible to reducevariation in resistance change characteristics between each bit causedby the base.

[Manufacturing Method]

FIG. 2( a) to (k) and FIGS. 3( a) and (b) are cross-sectional viewsshowing a method of manufacturing main parts of the nonvolatile memorydevice 10 in Embodiment 1 of the present invention. Furthermore, FIG. 4(a) to (e) are plan views showing the nonvolatile memory device 10 asseen from the top, corresponding to the processes from FIG. 2( h) toFIG. 3( a). The method of manufacturing the main parts of thenonvolatile memory device 10 shall be described using these figures.

First, as shown in FIG. 2( a), in a process of forming the first line101, the first line 101 is formed by forming a conductive layer (filmthickness: 400 to 600 nm) comprising aluminum, on the substrate 100 inwhich a transistor, a lower layer line, and so on are formed, andperforming patterning on the conductive layer.

Next, as shown in FIG. 2( b), in a process of forming the firstinterlayer insulating layer 102, the first interlayer insulating layer102 (film thickness: 500 to 1,000 nm) is formed by forming an insulatinglayer on the substrate 100 and covering the first line 101, andsubsequently planarizing the surface of the insulating layer. A plasmaTEOS film can be used for the first interlayer insulating layer 102.Furthermore, in order to reduce the amount of parasitic capacitancebetween lines, a fluorine-containing oxide (for example, FSG) or a low-kmaterial, and so on can be used for the first interlayer insulatinglayer 102.

Next, as shown in FIG. 2( c), in a process of forming the first contacthole 103, patterning is performed on the first interlayer insulatinglayer 102, using the desired mask, to form the first contact hole 103(diameter: 50 to 300 nmφ) which penetrates through the first interlayerinsulating layer 102 and reaches the first line 101. Here, when thewidth of the first line 101 is less than the diameter of the firstcontact hole 103, the area in which the first line 101 and the firstcontact plug 104 come into contact changes due to the impact of maskmisalignment, and thus, for example, cell current fluctuates. From thepoint of view of preventing the above, the width of the first line 101is made greater than the diameter of the first contact hole 103.

Next, in a process of forming the first contact plug 104, first, aTiN/Ti layer (film thickness: 5 to 30 nm) which functions as an adhesionlayer and a diffusion barrier is formed as a lower layer using thesputtering method, and tungsten (W, film thickness: 200 to 400 nm) whichserves as the main component is formed as an upper layer using the CVDmethod. As a result, as shown in FIG. 2( d), the first contact hole 103is filled with a conductive layer 104′ having a stacked structure, whichis to become the first contact plug 104. However, a depression (depth: 5to 100 nm) which reflects the shape of the base is created in the topplane of the conductive layer 104′ above the first contact hole 103.

Next, as shown in FIG. 2( e), in the process of forming the firstcontact plug 104, planarization polishing using the chemical mechanicalpolishing method (CMP method) is performed on the entire surface of thewafer to remove the unnecessary conductive material 104′ on the firstinterlayer insulating layer 102, and thus form the first contact plug104 inside the first contact hole 103. At this time, the top plane ofthe first contact plug 104 and the top plane of the first interlayerinsulating layer 102 are not continuous (that is, not on the sameplane), and a recess (depth: 5 to 50 nm) is created in thenon-continuous part. This is because, as an insulator and a conductor,respectively, the materials comprised in the first interlayer insulatinglayer 102 and the first contact plug 104 are necessarily different, andthus their polishing rates in the CMP method are different. This is anunavoidable phenomenon which necessarily occurs when using differenttypes of materials.

Next, as shown in FIG. 2( f), in a process of forming a conductive layer105′ (the lower electrode 105), the conductive layer 105′ (filmthickness: 50 to 200 nm) comprising a tantalum nitride and which laterbecomes the lower electrode 105 is formed with the sputtering method, onthe first interlayer insulating layer 102 and covering the first contactplug 104. The conductive layer 105′ is also formed in the part of therecess created above the first contact plug 104 inside the first contacthole 103. Furthermore, in the same manner as before, a depression whichreflects the shape of the base is created in the top plane of theconductive layer 105′ above the first contact plug 104.

Next, as shown in FIG. 2( g), in a process of forming a conductive layer105″ (the lower electrode 105), planarization polishing using the CMPmethod is performed on the entire surface of the wafer to form theconductive layer 105″ (film thickness: 20 to 100 nm) which becomes thelower electrode 105 after patterning. The point of this process is toperform planarization polishing on the conductive layer 105′ until theabove-described depression in the conductive layer 105′ created in FIG.2( f) disappears, and to leave behind the entire conductive layer 105″.According to such a manufacturing method, the step created above thefirst contact plug 4 is not transferred onto the surface of theconductive layer 105″, and thus the lower electrode 105 is extremelyflat throughout the entire surface, and a continuous plane is maintainedabove the first contact plug 104 and the first interlayer insulatinglayer 102. This is because, unlike when the contact plug 104 is formed,what is polished is always the same type of material because thepolishing of the conductive layer 105″ is stopped along the way, andthus, in principle, the difference in polishing rates in the CMP methodcan be avoided.

Next, as shown in FIG. 2( h) and FIG. 4( a), in a process of forming afirst variable resistance layer 106 a′, the first variable resistancelayer 106 a′ comprising a first transitional metal oxide is formed onthe conductive layer 105″. Here, the first variable resistance layer 106a′ is formed using what is called a reactive sputtering method in whichsputtering is performed on a tantalum target in an argon (Ar) and oxygengas atmosphere. The oxygen content of the first variable resistancelayer 106 a′ is 50 to 65 atm %, the resistivity is 2 to 50 mΩcm, and thefilm thickness is 20 to 100 nm.

Next, as shown in FIG. 2( i) and FIG. 4( b), in a process of forming thestep 106 ax in the first variable resistance layer 106 a′, the straightstep 106 ax (height: 1 to 30 nm) is formed, using the desired mask, inthe surface of the first variable resistance layer 106 a′ and extendingto an adjacent variable resistance element. On this occasion, it ispreferable that an inert gas such as Ar be used as the etching gas inorder to prevent fluorine (F), and so on, included in the etching gasfrom entering the first variable resistance layer 106 a′ and causingetching damage which causes the film property of the variable resistancelayer to deteriorate. Furthermore, it is also preferable to perform wetetching using an etching liquid containing hydrofluoric acid (HF) and soon. In this case, the fluorine (F) included in the etching liquid doesnot enter the variable resistance layer, and thus the variableresistance layer does not deteriorate.

Next, as shown in FIG. 2( j) and FIG. 4( c), in a process of forming asecond variable resistance layer 106 b′, the second variable resistancelayer 106 b′ comprising a second transitional metal oxide having ahigher oxygen content than the first transitional metal oxide (firstvariable resistance layer 106 a′) is formed on the first variableresistance layer 106 a′ and covering the step in the first variableresistance layer 106 a′. In the same manner as in the first variableresistance layer 106 a′, the second variable resistance layer 106 b′ isformed with the reactive sputtering method of performing sputtering on atantalum target in an oxygen gas atmosphere. The oxygen content of thesecond variable resistance layer 106 b′ is 67 to 71 atm %, theresistivity is 10⁷ mΩcm or greater, and the film thickness is 2 to 10nm. The bend 106 bx of the second variable resistance layer 106 b′ isformed above the step 106 ax in the surface of the first variableresistance layer 106 a′. Here, the film thickness of the bend 106 bx(the film thickness on the side wall of the step 106 ax) of the secondvariable resistance layer 106 b′ can be adjusted to be thin according tothe height of the step 106 ax base, and a thin-film part can be formedlocally in a stable manner. Furthermore, compared to the flat part ofthe second variable resistance layer 106 b′, the film property tends tobecome sparse in the bend 106 bx of the second variable resistance layer106 b′, and thus a film that allows easy breaking can be realized.Although the variable resistance layer is formed using reactivesputtering in the above-described process, a reactive sputtering methodof performing sputtering on a tantalum oxide target in an oxygen gasatmosphere may be used, and the variable resistance layer may be formedby plasma oxidation in an atmosphere that includes oxygen.

Next, as shown in FIG. 2( k) and FIG. 4( d), in a process of forming aconductive layer 107′ (the upper electrode 107), the conductive layer107′ comprising a noble metal (platinum, iridium, palladium, and so on)which becomes the upper electrode 107 after patterning is formed on thesecond variable resistance layer 106 b′.

Next, as shown in FIG. 3( a) and FIG. 4( e), in a process of forming thevariable resistance element, patterning using the desired mask isperformed on the conductive layer 105″, the first variable resistancelayer 106 a′, the second variable resistance layer 106 b′, and theconductive layer 107′ shown in FIG. 2( k) to form the variableresistance element in which the variable resistance layer 106 configuredof the stacked layers of the first variable resistance layer 106 a andthe second variable resistance layer 106 b is held between the lowerelectrode 105 and the upper electrode 107. Since etching is difficult toperform on a noble metal and the like which is typified as a materialhaving high standard electrode potential, when a noble metal is used forthe upper electrode 107, the variable resistance element can also beformed with such upper electrode 107 as a hard mask. Although, in thepresent process, patterning is performed collectively on the respectivelayers of the variable resistance element using the same mask,patterning may be performed on a per layer basis.

Lastly, as shown in FIG. 3( b), the second interlayer insulating layer108 (film thickness: 500 to 1000 nm) is formed covering the variableresistance element, and the second contact hole 109 and the secondcontact plug 110 are formed according to the same manufacturing methodas in FIGS. 2( b) and (c). Subsequently, the second line 111 is formedcovering the second contact plug 110, and the nonvolatile memory device10 is completed.

By adopting the above-described manufacturing method, it is possible toreflect the shape of the step of the surface of the first variableresistance layer 106 a and thereby stably form the bend 106 bx in thesecond variable resistance layer 106 b on the step 106 ax, and thus itis possible to cause the break phenomenon even with a low voltage, withthe bend 106 bx as a starting point of the initial break. Furthermore,since the step shape of the first variable resistance layer 106 a isformed in an intentional and controlled manner, the shape of the bend106 bx of the second variable resistance layer 106 b is stable, and thusvariation in initial break voltage does not increase. Therefore,lowering the break voltage and suppressing variation therein can both beachieved, and miniaturization and increased capacity of memories can berealized.

Embodiment 2

[Device Configuration]

FIG. 5( a) is a cross-sectional view of a nonvolatile memory device 20in Embodiment 2 of the present invention, and FIG. 5( b) is a plan viewof the first variable resistance layer 106 a included therein. In FIG.5, the same numerical references are used for elements that are the sameas in FIG. 1, and description thereof shall not be repeated.

As shown in FIGS. 5( a) and (b), the difference between the nonvolatilememory device 20 in Embodiment 2 and the nonvolatile memory device 10 inEmbodiment 1 is in the shape of the step that is formed in the firstvariable resistance layer 106 a. In the nonvolatile memory device 10,the step 106 ax formed in the surface of the first variable resistancelayer 106 a is straight-shaped, whereas, in the nonvolatile memorydevice 20, a ring-shaped step 106 ay (height: 1 to 30 nm, length: 250nm×4=1000 nm), that is, a depressed part is formed. Accordingly, a bend106 by of the second variable resistance layer 106 b is alsoring-shaped. In the present embodiment, a longer step pattern can beformed in one variable resistance element compared to the straight steppattern, and thus the region of the bend 106 by of the second variableresistance layer 106 b can be enlarged, and further lowering of thebreak voltage becomes possible because the region serving as thestarting point of the break phenomenon is augmented.

The step 106 ay is positioned between the first contact plug 104 and thesecond contact plug 110 (the first contact hole 103 and the secondcontact hole 109), and is a part which causes a change in elevation inthe interface between the first variable resistance layer 106 a and thesecond variable resistance layer 106 b. The step 106 ay is configured ofa side plane that connects a first principal plane and a secondprincipal plane lower than the first principal plane which serve asboundary planes between the first variable resistance layer 106 a andthe second variable resistance layer 106 b. This side plane is formed tohave, for example, a 90 degree angle with respect to one or both of thefirst principal plane and the second principal plane.

The step 106 ay is the part which includes an inflection point at whichthe flatness changes abruptly in the interface between the firstvariable resistance layer 106 a and the second variable resistance layer106 b, that is, a point at which the continuity of the flatness isinterrupted. When the first variable resistance layer 106 a and thesecond variable resistance layer 106 b are seen from above or below(when seen from the side in which the upper electrode 107 or the lowerelectrode 105 is provided), the step 106 ay is arranged in a ring-shape.It is preferable that the center of the ring-shaped step 106 ay beformed at the approximate center in the radial direction of the firstcontact hole 103 and the second contact hole 109.

The bend 106 by is positioned between the first contact plug 104 and thesecond contact plug 110 (the first contact hole 103 and the secondcontact hole 109), and is configured of a part of the second variableresistance layer 106 b which bends in the stacking direction of thefirst variable resistance layer 106 a and the second variable resistancelayer 106 b in the cross-sectional view. The bend 106 by is providedalong the step 106 ay, and is and is configured of a part above the sideplane of the step 106 ay.

According to this configuration, the bend 106 by of the second variableresistance layer 106 b is formed above the step 106 ay of the firstvariable resistance layer 106 a, and thus it is possible to cause thebreak phenomenon even with a low voltage, with the bend 106 by as astarting point of the initial break. Furthermore, since the shape of thestep of the first variable resistance layer 106 a is formed in anintentional and controlled manner, the shape of the bend 106 by of thesecond variable resistance layer 106 b is stable, and thus variation inbreak voltage does not increase. Although only one ring-shaped step 106ay is formed here, a plurality may be formed. Forming a plurality iseffective in terms of allowing the region serving as the starting pointof the break phenomenon to be enlarged. With this, lowering the breakvoltage and suppressing variation therein can both be achieved, andminiaturization and increased capacity of memories can be realized.

[Manufacturing Method]

FIG. 6( a) to (f) are cross-sectional views showing a method ofmanufacturing main parts of the nonvolatile memory device 20 inEmbodiment 2 of the present invention. Furthermore, FIG. 7( a) to (e)are plan views of the nonvolatile memory device 20 as seen from the top,corresponding to the processes shown in FIG. 6( a) to (e), respectively.The method of manufacturing the main parts of the nonvolatile memorydevice 20 shall be described using these figures. Furthermore, processesprior to FIG. 6( a) are the same as in FIG. 2( a) to (g), and thusdescription thereof shall not be repeated.

As shown in FIG. 6( a) and FIG. 7( a), in the process of forming thefirst variable resistance layer 106 a′, the first variable resistancelayer 106 a′ comprising a transitional metal oxide is formed on theconductive layer 105″. Here, the first variable resistance layer 106 a′is formed using what is called a reactive sputtering method in whichsputtering is performed on a tantalum target in an argon (Ar) and oxygengas atmosphere. The oxygen content of the first variable resistancelayer 106 a′ is 50 to 65 atm %, the resistivity is 2 to 50 mΩcm, and thefilm thickness is 20 to 100 nm.

Next, as shown in FIG. 6( b) and FIG. 7( b), in a process of forming thestep 106 ay in the first variable resistance layer 106 a′, thering-shaped step 106 ay (height: 1 to 30 nm) is formed, using thedesired mask, in the surface of the first variable resistance layer 106a′ such that one ring-shaped step 106 ay is always included during thesubsequent forming of the variable resistance element. On this occasion,it is preferable that an inert gas such as Ar be used as the etching gasin order to prevent fluorine (F), and so on, included in the etching gasfrom entering the first variable resistance layer 106 a′ and causingetching damage which causes the film property of the variable resistancelayer to deteriorate. Furthermore, it is also preferable to perform wetetching using an etching liquid containing hydrofluoric acid (HF) and soon. In this case, the fluorine (F) included in the etching liquid doesnot enter the variable resistance layer, and thus the variableresistance layer does not deteriorate.

FIG. 8A shows a cross-sectional view according to a SEM image takenimmediately after a ring-shaped step 106 ay is formed in the firstvariable resistance layer 106 a′ comprising a tantalum oxide (TaO_(x)).It can be seen that a ring-shaped step with a height of 30 nm and a ringdiameter of 250 nm is formed using a photo resist mask.

As shown in FIG. 6( c) and FIG. 7( c), in the process of forming thesecond variable resistance layer 106 b′, the second variable resistancelayer 106 b′ having a higher oxygen content than the first variableresistance layer 106 a′ is formed on the first variable resistance layer106 a′. In the same manner as in the first variable resistance layer 106a′, the second variable resistance layer 106 b′ is formed with thereactive sputtering method of performing sputtering on a tantalum targetin an oxygen gas atmosphere. The oxygen content of the second variableresistance layer 106 b′ is 67 to 71 atm %, the resistivity is 10⁷ mΩcmor greater, and the film thickness is 2 to 10 nm. The bend 106 by of thesecond variable resistance layer 106 b′ is formed above the step 106 ayin the surface of the first variable resistance layer 106 a′. Here, thefilm thickness of the bend 106 bx (the thickness on the side wall of thedepressed part of the first variable resistance layer 106 a′) of thesecond variable resistance layer 106 b′ can be adjusted to be thinaccording to the height of the step 106 ay base (the depth of thedepressed part), and a thin-film part can be formed locally in a stablemanner. Furthermore, compared to the flat part of the second variableresistance layer 106 b′, the film property tends to become sparse in thebend 106 by of the second variable resistance layer 106 b′, and thus afilm that allows easy breaking can be realized. Although the variableresistance layer is formed using reactive sputtering, a reactivesputtering method of performing sputtering on a tantalum oxide target inan oxygen gas atmosphere may be used, and the variable resistance layermay be formed by plasma oxidation in an atmosphere that includes oxygen.

Next, as shown in FIG. 6( d) and FIG. 7( d), in the process of formingthe conductive layer 107′ (the upper electrode 107), the conductivelayer 107′ comprising a noble metal (platinum (Pt), iridium (Ir),palladium (Pd), and so on) which becomes the upper electrode 107 afterpatterning is formed on the second variable resistance layer 106 b′.

Next, as shown in FIG. 6( e) and FIG. 7( e), in the process of formingthe variable resistance element, patterning using the desired mask isperformed on the conductive layer 105″, the first variable resistancelayer 106 a′, the second variable resistance layer 106 b′, and theconductive layer 107′ to form the variable resistance element in whichthe variable resistance layer 106 configured of the stacked layers ofthe first variable resistance layer 106 a and the second variableresistance layer 106 b is held between the lower electrode 105 and theupper electrode 107. As in Embodiment 1, in the case of the straightstep 106 ax, the etching volume with the step 106 ax as the axis isdifferent between the left and right and there is concern over etchingleft-over and base scraping due to over-etching. However, since thering-shaped step 106 ay is contained inside the variable resistanceelement, the volume of the first variable resistance layer 106 a′ to beetched does not change. In other words, etching left-over and basescraping due to over-etching do not occur easily, and thus manufacturingyield can be improved.

Lastly, as shown in FIG. 6( f), the second interlayer insulating layer108 (film thickness: 500 to 1000 nm) is formed covering the variableresistance element, and the second contact hole 109 and the secondcontact plug 110 are formed. Subsequently, the second line 111 is formedcovering the second contact plug 110, and the nonvolatile memory device20 is completed.

By adopting the above-described manufacturing method, it is possible toreflect the shape of the step of the surface of the first variableresistance layer 106 a and thereby stably form the bend 106 by in thesecond variable resistance layer 106 b on the step 106 ay, and thus itis possible to cause the break phenomenon even with a low voltage, withthe bend 106 bx as a starting point of the initial break. Furthermore,since the step shape of the first variable resistance layer 106 a isformed in an intentional and controlled manner, the shape of the bend106 by of the second variable resistance layer 106 b is stable, and thusvariation in initial break voltage does not increase. Therefore,lowering the break voltage and suppressing variation therein can both beachieved, and miniaturization and increased capacity of memories can berealized.

FIG. 8B is a graph showing the initial break voltage of theabove-described nonvolatile memory device 20. The graph also evaluatesthe initial break voltage required when the variable resistance elementand a load resistance of 5 kΩ are connected in series as in FIG. 19. InFIG. 8B, the break voltage is shown by standardizing, as 1.0, the breakvoltage of the nonvolatile memory device 60 in which a step is notformed in the first variable resistance layer 106 a. In the case of thenonvolatile memory device 20 in Embodiment 2 of the present invention(the case where a step is formed in the first variable resistance layer106 a), it can be seen that lowering of the break voltage is realized.Furthermore, because it can be inferred that the percentage for thelowering of the break voltage also tends to increase when the stepamount (the amount of the difference in elevation between the surfacesat the step 106 ay) is increased, it is also recognized that the breakvoltage can be controlled through the step amount.

Embodiment 3

[Device Configuration]

FIG. 9( a) is a cross-sectional view of a nonvolatile memory device 30in Embodiment 3 of the present invention, and FIG. 9( b) is a plan viewof the surface of the bottom electrode 105 included therein. In FIG. 9,the same numerical references are used for elements that are the same asin FIG. 1, and description thereof shall not be repeated.

As shown in FIGS. 9( a) and (b), the difference between the nonvolatilememory device 30 in Embodiment 3 and the nonvolatile memory device 10 inEmbodiment 1 is in the structure in which the first variable resistancelayer 106 a and the second variable resistance layer 106 b are in avertically-reversed placement. In the nonvolatile memory device 10, thebend 106 bx of the second variable resistance layer 106 b is formedabove the step 106 ax formed in the surface of the first variableresistance layer 106 a. In contrast, in the nonvolatile memory device30, the second variable resistance layer 106 b is formed on a straightstep 105 s formed in the surface (the interface with the second variableresistance layer 106 b) of the bottom electrode 105, and the firstvariable resistance layer 106 a is formed on the second variableresistance layer 106 b. The second variable resistance layer 106 b isformed covering the step 105 s, and a bend 106 bs is formed in thesecond variable resistance layer 106 b above the step 105 s. The upperelectrode 107 is formed on the first variable resistance layer 106 a.

The step 105 s is positioned between the first contact plug 104 and thesecond contact plug 110 (the first contact hole 103 and the secondcontact hole 109), and is a part which causes a change in elevation inthe interface between the lower electrode 105 and the second variableresistance layer 106 b. The step 105 s is configured of the side planeconnecting a first principal plane and a second principal plane lowerthan the first principal plane which serve as boundary planes betweenthe lower electrode 105 and the second variable resistance layer 106 b.This side plane is formed to have, for example, a 90 degree angle withrespect to one or both of the first principal plane and the secondprincipal plane.

The step 105 s is the part which includes an inflection point at whichthe flatness changes abruptly in the interface between the firstvariable resistance layer 106 a and the second variable resistance layer106 b, that is, a point at which the continuity of the flatness isinterrupted. When the bottom electrode 105 and the second variableresistance layer 106 b are seen from above or below (when seen from theside in which the upper electrode 107 or the lower electrode 105 isprovided), the step 105 s is arranged straightly. It is preferable thatthe step 105 s be formed at the approximate center of the widthdirection of the first contact hole 103 and the second contact hole 109.

The bend 106 bs is positioned between the first contact plug 104 and thesecond contact plug 110 (the first contact hole 103 and the secondcontact hole 109), and is a part of the second variable resistance layer106 b which bends in the stacking direction of the first variableresistance layer 106 a and the second variable resistance layer 106 b inthe cross-sectional view. The bend 106 bx is provided along the step 105s, and configured of a part above the side plane of the step 105 s.

According to this configuration, the bend 106 bs of the second variableresistance layer 106 b is formed above the step 105 s of the lowerelectrode 105, and thus it is possible to cause the break phenomenoneven with a low voltage, with the bend 106 bs as a starting point of theinitial break. Furthermore, since the step shape of the lower electrode105 is formed in an intentional and controlled manner, the shape of thebend 106 bs of the second variable resistance layer 106 b is stable, andthus variation in initial break voltage does not increase. Although onlyone straight step 105 s is formed here, a plurality may be formed.Forming a plurality is effective in terms of allowing the region servingas the starting point of the break phenomenon to be enlarged. With this,lowering the break voltage and suppressing variation therein can both beachieved, and miniaturization and increased capacity of memories can berealized.

[Manufacturing Method]

FIG. 10( a) to (g) are cross-sectional views showing a method ofmanufacturing main parts of the nonvolatile memory device 30 inEmbodiment 3 of the present invention. Furthermore, FIG. 11( a) to (f)are plan views of the nonvolatile memory device 30 as seen from the top,corresponding to the processes shown in FIG. 10( a) to (f),respectively. The method of manufacturing the main parts of thenonvolatile memory device 30 shall be described using these figures.Furthermore, processes prior to FIG. 10( a) are the same as shown inFIG. 2( a) to (f), and thus description thereof shall not be repeated.

As shown in FIG. 10( a) and FIG. 11( a), in the process of forming theconductive layer 105″ (the lower electrode 105), planarization polishingusing the chemical mechanical polishing method (CMP method) is performedon the entire surface of the wafer to form the conductive layer 105″(film thickness: 20 to 100 nm) which becomes the lower electrode 105after patterning.

Next, as shown in FIG. 10( b) and FIG. 11( b), in the process of formingthe step 105 s in the conductive layer 105″ (the lower electrode 105),the straight step 105 s (height: 1 to 30 nm) is formed, using thedesired mask, in the surface of the conductive layer 105″ and extendingto an adjacent variable resistance element. In order not to causeetching damage to the lower electrode 105, it is preferable that aninert gas such as Ar and the like be used as the etching gas.

As shown in FIG. 10( c) and FIG. 11( c), in the process of forming thesecond variable resistance layer 106 b′, the second variable resistancelayer 106 b′ comprising a second transitional metal oxide having ahigher oxygen content than a first transitional metal oxide (firstvariable resistance layer 106 a′) is formed on the conductive layer 105″and covering the step of the conductive layer 105″. Here, the secondvariable resistance layer 106 b′ is formed using what is called areactive sputtering method in which sputtering is performed on atantalum target in an oxygen gas atmosphere. The oxygen content of thesecond variable resistance layer 106 b′ is 67 to 71 atm %, theresistivity is 10⁷ mΩcm or greater, and the film thickness is 2 to 10nm. The bend 106 bs of the second variable resistance layer 106 b′ isformed above the step 105 s on the surface of the conductive layer 105″.Here, the film thickness of the bend 106 bs (the film thickness on theside wall of the step 105 s) of the second variable resistance layer 106b′ can be adjusted to be thin according to the height of the step 105 sbase, and a thin-film part can be formed locally in a stable manner.Furthermore, compared to the flat part of the second variable resistancelayer 106 b′, the film property tends to become sparse in the bend 106bs of the second variable resistance layer 106 b′, and thus a film thatallows easy breaking can be realized. Although the variable resistancelayer is formed using reactive sputtering in the above-describedprocess, the variable resistance layer may be formed by using a reactivesputtering method of performing sputtering on a tantalum oxide target inan oxygen gas atmosphere.

Next, as shown in FIG. 10( d) and FIG. 11( d), in the process of formingthe first variable resistance layer 106 a′, the first variableresistance layer 106 a′ comprising the first transitional metal oxide isformed on the second variable resistance layer 106 b′. As in theprevious description, the first variable resistance layer 106 a′ isformed using what is called a reactive sputtering method in whichsputtering is performed on a tantalum target in an argon (Ar) and oxygengas atmosphere. The oxygen content of the first variable resistancelayer 106 a′ is 50 to 65 atm %, the resistivity is 2 to 50 mΩcm, and thefilm thickness is 20 to 100 nm.

Next, as shown in FIG. 10( e) and FIG. 11( e), in the process of forminga conductive layer 107′ (the upper electrode 107), the conductive layer107′ comprising a noble metal (platinum, iridium, palladium, and so on)which becomes the upper electrode 107 after patterning is formed on thefirst variable resistance layer 106 a′.

Next, as shown in FIG. 10( f) and FIG. 11( f), in the process of formingthe variable resistance element, patterning using the desired mask isperformed on the conductive layer 105″, the second variable resistancelayer 106 b′, the first variable resistance layer 106 a′, and theconductive layer 107′ to form the variable resistance element in whichthe variable resistance layer 106 configured of the stacked layers ofthe second variable resistance layer 106 b and the first variableresistance layer 106 a is held between the lower electrode 105 and theupper electrode 107.

Lastly, as shown in FIG. 10( g), the second interlayer insulating layer108 (film thickness: 500 to 1000 nm) is formed covering the variableresistance element, and the second contact hole 109 and the secondcontact plug 110 are formed. Subsequently, the second line 111 is formedcovering the second contact plug 110, and the nonvolatile memory device30 is completed.

By adopting the above-described manufacturing method, it is possible toreflect the shape of the step of the lower electrode 105 and therebystably form the bend 106 bs in the second variable resistance layer 106b on the step 105 s, and thus it is possible to cause the breakphenomenon even with a low voltage, with the bend 106 bs as a startingpoint of the initial break. Furthermore, since the step shape of thelower electrode 105 is formed in an intentional and controlled manner,the shape of the bend 106 bs of the second variable resistance layer 106b is stable, and thus variation in break voltage does not increase.Therefore, lowering the break voltage and suppressing variation thereincan both be achieved, and miniaturization and increased capacity ofmemories can be realized.

Embodiment 4

[Device Configuration]

FIG. 12( a) is a cross-sectional view of a nonvolatile memory device 40in Embodiment 4 of the present invention, and FIG. 12( b) is a plan viewof the surface of the lower electrode 105 included therein. In FIG. 12,the same numerical references are used for elements that are the same asin FIG. 9, and description thereof shall not be repeated.

As shown in FIGS. 12( a) and (b), the difference between the nonvolatilememory device 40 in Embodiment 4 and the nonvolatile memory device 30 inEmbodiment 3 is in the shape of the step that is formed in the lowerelectrode 105. In the nonvolatile memory device 30, the straight step105 s is formed on the surface of the lower electrode 105, whereas, inthe nonvolatile memory device 40, a ring-shaped step 105 t (height: 1 to30 nm, length: 250 nm×4=1000 nm), that is, a depressed part is formed.Accordingly, a bend 106 bt of the second variable resistance layer 106 bis also ring-shaped. In the present embodiment, a longer step patterncan be formed in one variable resistance element compared to thestraight step pattern, and thus the region of the bend 106 bt of thesecond variable resistance layer 106 b can be enlarged, and furtherlowering of the break voltage becomes possible because the regionserving as the starting point of the break phenomenon is augmented.

The step 105 t is positioned between the first contact plug 104 and thesecond contact plug 110 (the first contact hole 103 and the secondcontact hole 109), and is a part which causes a change in elevation inthe interface between the lower electrode 105 and the second variableresistance layer 106 b. The step 105 t is configured of the side planeconnecting a first principal plane and a second principal plane lowerthan the first principal plane which serve as boundary planes betweenthe lower electrode 105 and the second variable resistance layer 106 b.This side plane is formed to have a 90 degree angle with respect to oneor both of the first principal plane and the second principal plane.

The step 105 t is the part which includes an inflection point at whichthe flatness changes abruptly in the interface between the firstvariable resistance layer 106 a and the second variable resistance layer106 b, that is, a point at which the continuity of the flatness isinterrupted. When the lower electrode 105 and the second variableresistance layer 106 b are seen from above or below (when seen from theside in which the upper electrode 107 or the lower electrode 105 isprovided), the step 105 t is arranged in a ring-shape. It is preferablethat the center of the ring-shaped step 105 t be formed at theapproximate center in the radial direction of the first contact hole 103and the second contact hole 109.

The bend 106 bt is positioned between the first contact plug 104 and thesecond contact plug 110 (the first contact hole 103 and the secondcontact hole 109), and is a part of the second variable resistance layer106 b which bends in the stacking direction of the first variableresistance layer 106 a and the second variable resistance layer 106 b inthe cross-sectional view. The bend 106 bt is provided along the step 105t, and configured of a part above the side plane of the step 105 t.

According to this configuration, it is possible to reflect the shape ofthe step of the lower electrode 105 and thereby stably form the bend 106bt in the second variable resistance layer 106 b on the step 105 t, andthus it is possible to cause the break phenomenon even with a lowvoltage, with the bend 106 bt as a starting point of the initial break.Furthermore, since the step shape of the lower electrode 105 is formedin an intentional and controlled manner, the shape of the bend 106 bt ofthe second variable resistance layer 106 b is stable, and thus variationin break voltage does not increase. Although only one ring-shaped step105 t is formed here, a plurality may be formed. Forming a plurality iseffective in terms of allowing the region serving as the starting pointof the break phenomenon to be enlarged. With this, lowering the breakvoltage and suppressing variation therein can both be achieved, andminiaturization and increased capacity of memories can be realized.

[Manufacturing Method]

FIG. 13( a) to (g) are cross-sectional views showing a method ofmanufacturing main parts of the nonvolatile memory device 40 inEmbodiment 4 of the present invention. Furthermore, FIG. 14( a) to (f)are plan views of the nonvolatile memory device 40 as seen from the top,corresponding to the processes shown in FIG. 13( a) to (f),respectively. The method of manufacturing the main parts of thenonvolatile memory device 40 shall be described using these figures.Furthermore, processes prior to FIG. 13( a) are the same as shown inFIG. 2( a) to (f), and thus description thereof shall not be repeated.

As shown in FIG. 13( a) and FIG. 14( a), in the process of forming theconductive layer 105″ (the lower electrode 105), planarization polishingusing the chemical mechanical polishing method (CMP method) is performedon the entire surface of the wafer to form the conductive layer 105″(film thickness: 20 to 100 nm) which becomes the lower electrode 105after patterning.

Next, as shown in FIG. 13( b) and FIG. 14( b), in the process of formingthe step 105 t in the conductive layer 105″ (the lower electrode 105),the ring-shaped step 105 t (height: 1 to 30 nm) is formed, using thedesired mask, in the surface of the conductive layer 105″ such that onering-shaped step 105 t is always included during the subsequent formingof the variable resistance element. In order not to cause etching damageto the lower electrode 105, it is preferable that an inert gas such asAr and the like be used as the etching gas.

FIG. 15 shows a cross-sectional view according to a SEM image takenimmediately after the ring-shaped step 105 t is formed in the conductivelayer 105″ (the lower electrode 105) comprising a tantalum nitride. Itcan be seen that the ring-shaped step 105 t having a height of 20 nm anda ring diameter of 250 nm is formed using a photo resist mask.

As shown in FIG. 13( c) and FIG. 14( c), in the process of forming thesecond variable resistance layer 106 b′, the second variable resistancelayer 106 b′ having a higher oxygen content than the first variableresistance layer 106 a′ is formed on conductive layer 105″. Here, thesecond variable resistance layer 106 b′ is formed using what is called areactive sputtering method in which sputtering is performed on atantalum target in an oxygen gas atmosphere. The oxygen content of thesecond variable resistance layer 106 b′ is 67 to 71 atm %, theresistivity is 10⁷ mΩcm or greater, and the film thickness is 2 to 10nm. Here, the film thickness of the bend 106 bt (the film thickness onthe side wall of the depressed part of the conductive layer 105″) of thesecond variable resistance layer 106 b′ can be adjusted to be thinaccording to the height of the step 105 t base (the depth of thedepressed part), and a thin-film part can be formed locally in a stablemanner. Furthermore, compared to the flat part of the second variableresistance layer 106 b′, the film property tends to become sparse in thebend 106 bt of the second variable resistance layer 106 b′, and thus afilm that allows easy breaking can be realized. Although the variableresistance layer is formed using reactive sputtering in theabove-described process, a reactive sputtering method of performingsputtering on a tantalum oxide target in an oxygen gas atmosphere may beused, and the variable resistance layer may be formed using the CVDmethod.

Next, as shown in FIG. 13( d) and FIG. 14( d), in the process of formingthe first variable resistance layer 106 a′, the first variableresistance layer 106 a′ comprising a transitional metal oxide is formedon the second variable resistance layer 106 b′. As in the previousdescription, the first variable resistance layer 106 a′ is formed usingwhat is called a reactive sputtering method in which sputtering isperformed on a tantalum target in an argon (Ar) and oxygen gasatmosphere. The oxygen content of the first variable resistance layer106 a′ is 50 to 65 atm %, the resistivity is 2 to 50 mΩcm, and the filmthickness is 20 to 100 nm.

Next, as shown in FIG. 13( e) and FIG. 14( e), in the process of formingthe conductive layer 107′ (the upper electrode 107), the conductivelayer 107′ comprising a noble metal (platinum (Pt), iridium (Ir),palladium (Pd), and so on) which becomes the upper electrode 107 afterpatterning is formed on the first variable resistance layer 106 a′.

Next, as shown in FIG. 13( f) and FIG. 14( f), in the process of formingthe variable resistance element, patterning using the desired mask isperformed on the conductive layer 105″, the second variable resistancelayer 106 b′, the first variable resistance layer 106 a′, and theconductive layer 107′ to form the variable resistance element in whichthe variable resistance layer 106 configured of the stacked layers ofthe second variable resistance layer 106 b and the first variableresistance layer 106 a is held between the lower electrode 105 and theupper electrode 107. As in Embodiment 3, in the case of the straightstep 105 s, the etching volume with the step 105 s as the axis isdifferent between the left and right and there is concern over etchingleft-over and base scraping due to over-etching. However, since thering-shaped step 105 t is contained inside the variable resistanceelement, the volume of the conductive layer 105″ to be etched does notchange. In other words, etching left-over and base scraping due toover-etching do not occur easily, and thus manufacturing yield can beimproved.

Lastly, as shown in FIG. 13( g), the second interlayer insulating layer108 (film thickness: 500 to 1000 nm) is formed covering the variableresistance element, and the second contact hole 109 and the secondcontact plug 110 are formed. Subsequently, the second line 111 is formedcovering the second contact plug 110, and the nonvolatile memory device40 is completed.

By adopting the above-described manufacturing method, it is possible toreflect the shape of the step of the lower electrode 105 and therebystably form the bend 106 bt in the second variable resistance layer 106b on the step 105 t, and thus it is possible to cause the breakphenomenon even with a low voltage, with the bend 106 bt as a startingpoint of the initial break. Furthermore, since the step shape of thelower electrode 105 is formed in an intentional and controlled manner,the shape of the bend 106 bt of the second variable resistance layer 106b is stable, and thus variation in break voltage does not increase.Therefore, lowering the break voltage and suppressing variation thereincan both be achieved, and miniaturization and increased capacity ofmemories can be realized.

Embodiment 5

[Device Configuration]

FIG. 16( a) is a cross-sectional view of a nonvolatile memory device 41in Embodiment 5 of the present invention, FIG. 16( b) is a plan view ofthe first variable resistance layer 106 a included therein, and FIG. 16(c) is a perspective view of the first variable resistance layer 106 a.In FIG. 16, the same numerical references are used for elements that arethe same as in FIG. 1, and description thereof shall not be repeated.

As shown in FIGS. 16( a), (b), and (c), the difference between thenonvolatile memory device 41 in Embodiment 5 and the nonvolatile memorydevice 10 in Embodiment 1 is in the shape of the step formed in thefirst variable resistance layer 106 a. Specifically, in the nonvolatilememory device 10, the step 106 ax formed in the surface of the firstvariable resistance layer 106 a is a single straight step, whereas, inthe nonvolatile memory device 41, the plural (two) straight steps of astep 106 ax 1 and a step 106 ax 2 formed in the surface of the firstvariable resistance layer 106 a are formed, and a crossing point atwhich the plural steps cross is formed at the central part of theelement. The first variable resistance layer 106 a is segmented intofour regions having the crossing point as a center. As the step amountswhen the region in the back left of the first variable resistance layer106 a is taken as a reference, the difference with the forward leftplanar region of the first variable resistance layer 106 a is 10 nm, thedifference with the back right planer portion is 10 nm, and thedifference with the forward right planar region is 20 nm.

The steps 106 ax 1 and 106 ax 2 are positioned between the first contactplug 104 and the second contact plug 110 (the first contact hole 103 andthe second contact hole 109), and are parts which cause a change inelevation in the interface between the first variable resistance layer106 a and the second variable resistance layer 106 b. The step 106 ax 1and 106 ax 2 are each configured of side planes connecting a firstprincipal plane and a second principal plane lower than the firstprincipal plane which serve as boundary planes between the firstvariable resistance layer 106 a and the second variable resistance layer106 b. These side planes are formed to have, for example, a 90 degreeangle with respect to one or both of the first principal plane and thesecond principal plane.

The steps 106 ax 1 and 106 ax 2 are parts which include an inflectionpoint at which the flatness changes abruptly in the interface betweenthe first variable resistance layer 106 a and the second variableresistance layer 106 b, that is, a point at which the continuity of theflatness is interrupted. When the first variable resistance layer 106 aand the second variable resistance layer 106 b are seen from above orbelow (when seen from the side in which the upper electrode 107 or thelower electrode 105 is provided), the steps 106 ax 1 and 106 ax 2 arearranged in respective lines and cross each other in the shape of across. It is preferable that the steps 106 ax 1 and 106 ax 2 be formedat the approximate center in the radial direction of the first contacthole 103 and the second contact hole 109.

The bend 106 bx is positioned between the first contact plug 104 and thesecond contact plug 110 (the first contact hole 103 and the secondcontact hole 109), and is a part of the second variable resistance layer106 b which bends in the stacking direction of the second variableresistance layer 106 b in the cross-sectional view. The bend 106 bx isprovided along the step 106 ax 1 and 106 ax 2.

According to this configuration, the bend 106 bx of the second variableresistance layer 106 b is formed above the crossing point of the steps106 ax 1 and 106 ax 2 of the first variable resistance layer 106 a, andthus it is possible to cause the break phenomenon even with a lowvoltage, with the bend 106 bx as a starting point of the initial break.Furthermore, the electric field is easily concentrated at the crossingpoint, and thus allowing the location of the break phenomenon to befixed. Therefore, by placing the crossing point at the central part ofthe variable resistance element and away from the edges of the variableresistance element, a filament can be formed at a part that is minimallyaffected by etching damage and an oxidized region of a layer insulatingfilm and the like. Accordingly, variation in resistance changecharacteristics is greatly reduced, and thus it is possible to realize anonvolatile memory device having little bit variation and excellentmanufacturing yield.

[Manufacturing Method]

FIG. 17( a) to (g) are cross-sectional views showing a method ofmanufacturing main parts of the nonvolatile memory device 41 inEmbodiment 5 of the present invention. Furthermore, FIG. 18( a) to (c)show perspective views of the first variable resistance layer 106 a′.The method of manufacturing the main parts of the nonvolatile memorydevice 41 shall be described using these figures. Furthermore, processesprior to FIG. 17( a) are the same as shown in FIG. 2( a) to (g), andthus description thereof shall not be repeated.

As shown in FIG. 17( a) and FIG. 18( a), in the process of forming thefirst variable resistance layer 106 a′, the first variable resistancelayer 106 a′ comprising a transitional metal oxide is formed on theconductive layer 105″. Here, the first variable resistance layer 106 a′is formed using what is called a reactive sputtering method in whichsputtering is performed on a tantalum target in an argon (Ar) and oxygengas atmosphere. The oxygen content of the first variable resistancelayer 106 a′ is 50 to 65 atm %, the resistivity is 2 to 50 mΩcm, and thefilm thickness is 20 to 100 nm.

Next, as shown in FIG. 17( b) and FIG. 18( b), in a process of formingthe step 106 ax 1 in the first variable resistance layer 106 a′, thestraight (a line-shape running in the on-paper vertical direction ofFIG. 17) step 106 ax 1 (height: 10 nm) is formed extending to anadjacent variable resistance element, using the desired mask.

Next, as shown in FIG. 17( c) and FIG. 18( c), in a process of formingthe step 106 ax 2 in the first variable resistance layer 106 a′, thestraight step 106 ax 2 (height: 10 nm) is formed in a direction thatcrosses the step 106 ax 1 (the on-paper horizontal direction of FIG.17), using the desired mask. With this, the two straight steps of thestep 106 ax 1 and step 106 ax 2 are formed in the surface of the firstvariable resistance layer 106 a′, and thus a crossing point in whichsteps cross is formed at the central part of the element. Four regionshaving the crossing point as a center are formed in the first variableresistance layer 106 a′. When the region in the back left of the firstvariable resistance layer 106 a′ is taken as a reference, a 10 nmdifference in elevation is created with the forward left planar regionand the back right planar region of the first variable resistance layer106 a′ that have been etched once, and a 20 nm difference in elevationis created with the forward right planar region which is etched twice.

In the etching for forming the above-described steps 106 ax 1 and 106 ax2, it is preferable that an inert gas such as Ar be used as the etchinggas in order to prevent fluorine (F), and so on, included in the etchinggas from entering the first variable resistance layer 106 a′ and causingetching damage which causes the film property of the variable resistancelayer to deteriorate. Furthermore, it is also preferable to perform wetetching using an etching liquid containing hydrofluoric acid (HF) and soon. In this case, the fluorine (F) included in the etching liquid doesnot enter the variable resistance layer, and thus the variableresistance layer does not deteriorate.

As shown in FIG. 17( d), in the process of forming the second variableresistance layer 106 b′, the second variable resistance layer 106 b′having a higher oxygen content than the first variable resistance layer106 a′ is formed on the first variable resistance layer 106 a′. In thesame manner as in the first variable resistance layer 106 a′, the secondvariable resistance layer 106 b′ is formed with the reactive sputteringmethod of performing sputtering on a tantalum target in an oxygen gasatmosphere. The oxygen content of the second variable resistance layer106 b′ is 67 to 71 atm %, the resistivity is 10⁷ mΩcm or greater, andthe film thickness is 2 to 10 nm. The bend 106 bx of the second variableresistance layer 106 b′ is formed above the steps 106 ax 1 and 106 ax 2in the surface of the first variable resistance layer 106 a′. Here, thefilm thickness of the bend 106 bx (the film thickness on the side wallof the steps 106 ax 1 and 106 ax 2) of the second variable resistancelayer 106 b′ can be adjusted to be thin according to the height of thesteps 106 ax 1 and 106 ax 2 base, and a thin-film part can be formedlocally in a stable manner. Furthermore, compared to the flat part ofthe second variable resistance layer 106 b′, the film property tends tobecome sparse in the bend 106 bx of the second variable resistance layer106 b′, and thus a film that allows easy breaking can be realized.Although the variable resistance layer is formed using reactivesputtering, a reactive sputtering method of performing sputtering on atantalum oxide target in an oxygen gas atmosphere may be used, and thevariable resistance layer may be formed by plasma oxidation in anatmosphere that includes oxygen.

Next, as shown in FIG. 17( e), in the process of forming the conductivelayer 107′ (the upper electrode 107), the conductive layer 107′comprising a noble metal (platinum (Pt), iridium (Ir), palladium (Pd),and so on) which becomes the upper electrode 107 after patterning isformed on the second variable resistance layer 106 b′.

Next, as shown in FIG. 17( f), in the process of forming the variableresistance element, patterning using the desired mask is performed onthe conductive layer 105″, the first variable resistance layer 106 a′,the second variable resistance layer 106 b′, and the conductive layer107′ to form the variable resistance element in which the variableresistance layer 106 configured of the stacked layers of the firstvariable resistance layer 106 a and the second variable resistance layer106 b is held between the lower electrode 105 and the upper electrode107.

Lastly, as shown in FIG. 17( g), the second interlayer insulating layer108 (film thickness: 500 to 1000 nm) is formed covering the variableresistance element, and the second contact hole 109 and the secondcontact plug 110 are formed. Subsequently, the second line 111 is formedcovering the second contact plug 110, and the nonvolatile memory device41 is completed.

By adopting the above-described manufacturing method, it is possible tomake use of the shape of the steps in the surface of the first variableresistance layer 106 a to intentionally form, in the second variableresistance layer 106 b formed in the crossing point at which the stepscross, a region where electric fields easily concentrate. By placing thecrossing point at the central part of the variable resistance elementand away from the edges of the variable resistance element, a filamentcan be formed at a part that is minimally affected by etching damage andan oxidized region of a layer insulating film and the like. Accordingly,variation in resistance change characteristics is greatly reduced, andthus it is possible to realize a nonvolatile memory device having littlebit variation and excellent manufacturing yield.

It should be noted that, although the step 106 ax 1 and the step 106 ax2 are straight-shaped in the present embodiment, they may also bering-shaped. Furthermore, the vertical placement of the first variableresistance layer 106 a and the second variable resistance layer 106 bmay be reversed. Specifically, the steps 106 ax 1 and 106 ax 2 may beformed in the interface between the lower electrode 105 and the secondvariable resistance layer 106 b, and second variable resistance layer106 b may be formed covering the steps 106 ax 1 and 106 ax 2 and havethe bend 106 bx on the crossing point of the steps 106 ax 1 and 106 ax2.

Embodiment 6

[Device Configuration]

FIG. 19( a) is a cross-sectional view of a nonvolatile memory device 42in Embodiment 6 of the present invention, and (b) is a plan view of thefirst variable resistance layer 106 a included therein. In FIG. 19, thesame numerical references are used for elements that are the same as inFIG. 1, and description thereof shall not be repeated.

As shown in FIGS. 19( a) and (b), the difference between the nonvolatilememory device 42 in Embodiment 6 and the nonvolatile memory device 20 inEmbodiment 2 is in the particular manner in which the ring-shaped stepis shaped so that the difference between a thick-film part and athin-film part of the second variable resistance layer 106 b is furtherincreased. In the nonvolatile memory device 20, the ring-shaped step 106ay is formed in the surface of the first variable resistance layer 106a, whereas, in the nonvolatile memory device 42, a ring-shaped step 106az, that is, a depressed part is formed in the surface of the stackedstructure of the first variable resistance layer 106 a and a secondvariable resistance layer 106 b 1. The ring-shaped step 106 az is formedby removing a part of the first variable resistance layer 106 a and thesecond variable resistance layer 106 b 1. In addition, a second variableresistance layer 106 b 2 is additionally-stacked to cover thering-shaped step 106 az. Accordingly, in the nonvolatile memory device20, the localized difference in film thickness in the second variableresistance layer 106 b results from the step coatability of the secondvariable resistance layer 106 b caused by the ring-shaped step 106 azand is thus small, whereas in the nonvolatile memory device 42, thesecond variable resistance layer 106 b 1 remains in the region otherthan the ring-shaped step 106 az at the time of forming the secondvariable resistance layer 106 b 2, and thus the difference in filmthickness of the second variable resistance layer 106 b is bigger by asmuch as the film thickness of the second variable resistance layer 106 b1.

The step 106 az is positioned between the first contact plug 104 and thesecond contact plug 110 (the first contact hole 103 and the secondcontact hole 109), and is a part which causes a change in elevation inthe interface between the first variable resistance layer 106 a and thesecond variable resistance layer 106 b. The step 106 az is configured ofa side plane that connects a first principal plane and a secondprincipal plane lower than the first principal plane which serve asboundary planes between the first variable resistance layer 106 a andthe second variable resistance layer 106 b. The step 106 az is formedsuch that this side plane forms a 90 degree angle with respect to one orboth of the first principal plane and the second principal plane.

The step 106 az is the part which includes an inflection point at whichthe flatness changes abruptly in the interface between the firstvariable resistance layer 106 a and the second variable resistance layer106 b, that is, a point at which the continuity of the flatness isinterrupted. When the first variable resistance layer 106 a and thesecond variable resistance layer 106 b are seen from above or below(when seen from the side in which the upper electrode 107 or the lowerelectrode 105 is provided), the step 106 az is arranged in a ring-shape.It is preferable that the center of the ring-shaped step 106 az beformed at the approximate center in the radial direction of the firstcontact hole 103 and the second contact hole 109.

The bend 106 by is positioned between the first contact plug 104 and thesecond contact plug 110 (the first contact hole 103 and the secondcontact hole 109), and is configured of a part of the second variableresistance layer 106 b which bends in the stacking direction of thefirst variable resistance layer 106 a and the second variable resistancelayer 106 b in the cross-sectional view. The bend 106 by is providedalong the step 106 az, and is and is configured of a part above the sideplane of the step 106 az.

According to this configuration, the bend 106 by is formed in the secondvariable resistance layer 106 b, and thus it is possible to cause thebreak phenomenon even with a low voltage, with the bend 106 by as astarting point of the initial break. Furthermore, since the secondvariable resistance layer 106 b 1 remains in the region other than thering-shaped step 106 az at the time of forming the second variableresistance layer 106 b 2, it is possible to increase the film thicknessof the second variable resistance layer 106 b and significantly reduceleak currents, and thus voltage can be more reliably applied to the celland further lowering of the break voltage becomes possible. With this,lowering the break voltage and suppressing variation therein can both beachieved, and miniaturization and increased capacity of memories can berealized.

[Manufacturing Method]

FIG. 20( a) to (g) are cross-sectional views showing a method ofmanufacturing main parts of the nonvolatile memory device 42 inEmbodiment 6 of the present invention. The method of manufacturing themain parts of the nonvolatile memory device 42 shall be described usingthis figure. Furthermore, processes prior to FIG. 20( a) are the same asshown in FIG. 2( a) to (g), and thus description thereof shall not berepeated.

As shown in FIG. 20( a), in the process of forming the first variableresistance layer 106 a′, the first variable resistance layer 106 a′comprising a first transitional metal oxide is formed on the conductivelayer 105″. Here, the first variable resistance layer 106 a′ is formedusing what is called a reactive sputtering method in which sputtering isperformed on a tantalum target in an argon (Ar) and oxygen gasatmosphere. The oxygen content of the first variable resistance layer106 a′ is 50 to 65 atm %, the resistivity is 2 to 50 mΩcm, and the filmthickness is 20 to 100 nm.

As shown in FIG. 20( b), in a process of forming the second variableresistance layer 106 b 1′, the second variable resistance layer 106 b 1′comprising a second transitional metal oxide having a higher oxygencontent than the first transitional metal oxide (first variableresistance layer 106 a′) is formed on the first variable resistancelayer 106 a′. In the same manner as in the first variable resistancelayer 106 a′, the second variable resistance layer 106 b 1′ is formedwith the reactive sputtering method of performing sputtering on atantalum target in an oxygen gas atmosphere. The oxygen content of thesecond variable resistance layer 106 b 1′ is 67 to 71 atm %, theresistivity is 10⁷ mΩcm or greater, and the film thickness is 2 to 10nm. Although the variable resistance layer is formed using reactivesputtering, a reactive sputtering method of performing sputtering on atantalum oxide target in an oxygen gas atmosphere may be used, and thevariable resistance layer may be formed by plasma oxidation in anatmosphere that includes oxygen.

Next, as shown in FIG. 20( c), in a process of forming the step 106 ayin the stacked structure of the first variable resistance layer 106 a′and the second variable resistance layer 106 b 1′ (the surface of thesecond variable resistance layer 106 b 1′), the ring-shaped step 106 ay(height: 2 to 30 nm) is formed, using the desired mask, such that onering-shaped step 106 ay is always included during the subsequent formingof the variable resistance element (during the forming of the secondvariable resistance layer 106 b′). In this case, in the ring-shaped step106 ay, the second variable resistance layer 106 b 1′ is certainlyremoved, that is, a through-hole that reaches up to the first variableresistance layer 106 a′ is formed in the second variable resistancelayer 106 b 1′, and a part of the first variable resistance layer 106 a′is removed. Furthermore, on this occasion, it is preferable that aninert gas such as Ar be used as the etching gas in order to preventfluorine (F), and so on, included in the etching gas from entering thefirst variable resistance layer 106 a′ and causing etching damage whichcauses the film property of the variable resistance layer todeteriorate. Furthermore, it is also preferable to perform wet etchingusing an etching liquid containing hydrofluoric acid (HF) and so on. Inthis case, the fluorine (F) included in the etching liquid does notenter the variable resistance layer, and thus the variable resistancelayer does not deteriorate.

Next, as shown in FIG. 20( d), in a process of forming the secondvariable resistance layer 106 b 2′, the second variable resistance layer106 b 2′ comprising a second transitional metal oxide having a higheroxygen content than the first transitional metal oxide is formed on thering-shaped step 106 ay of the second variable resistance layer 106 b 1′and the first variable resistance layer 106 a′. In this case, the secondvariable resistance layer 106 b 2′ is additionally stacked on the secondvariable resistance layer 106 b 1′ and the first variable resistancelayer 106 a′ and covering the step 106 ay. The film forming method isthe same as in the second variable resistance film 106 b 1′. The bend106 by of the second variable resistance layer 106 b 2′ is formed on thering-shaped step 106 ay. Compared to the film thickness of the secondvariable resistance layer 106 b 2′ inside the ring-shaped step 106 ay,the difference in the film thickness of the second variable resistancelayer 106 b is increased by as much as the film thickness of the secondvariable resistance layer 106 b 1′ remaining in the region other thanthe ring-shaped step ay at the time of forming the second variableresistance layer 106 b 2.

Next, as shown in FIG. 20( e), in the process of forming the conductivelayer 107′ (the upper electrode 107), the conductive layer 107′comprising a noble metal (platinum (Pt), iridium (Ir), palladium (Pd),and so on) which becomes the upper electrode 107 after patterning isformed on the second variable resistance layer 106 b′.

Next, as shown in FIG. 20( f), in the process of forming the variableresistance element, patterning using the desired mask is performed onthe conductive layer 105″, the first variable resistance layer 106 a′,the second variable resistance layer 106 b′, and the conductive layer107′ to form the variable resistance element in which the variableresistance layer 106 configured of the stacked layers of the firstvariable resistance layer 106 a and the second variable resistance layer106 b is held between the lower electrode 105 and the upper electrode107. As in Embodiment 1, in the case of the straight step 106 ax, theetching volume with the step 106 ax as the axis is different between theleft and right and there is concern over etching left-over and basescraping due to over-etching. However, since the ring-shaped step 106 ayis contained inside the variable resistance element, the volume of thefirst variable resistance layer 106 a to be etched does not change. Inother words, etching left-over and base scraping due to over-etching donot occur easily, and thus manufacturing yield can be improved.

Lastly, as shown in FIG. 20( g), the second interlayer insulating layer108 (film thickness: 500 to 1000 nm) is formed covering the variableresistance element, and the second contact hole 109 and the secondcontact plug 110 are formed. Subsequently, the second line 111 is formedcovering the second contact plug 110, and the nonvolatile memory device42 is completed.

By adopting the above-described manufacturing method, it is possible toreflect the shape of the step of the surface of the first variableresistance layer 106 a and thereby stably form the bend 106 by in thesecond variable resistance layer 106 b on the step 106 ay, and thus itis possible to cause the break phenomenon even with a low voltage, withthe bend 106 by as a starting point of the initial break. Furthermore,since the step shape of the first variable resistance layer 106 a isformed in an intentional and controlled manner, the shape of the bend106 by of the second variable resistance layer 106 b is stable, and thusvariation in initial break voltage does not increase. Furthermore, sincethe second variable resistance layer 106 b 1 remains in the region otherthan the ring-shaped step 106 az at the time of forming the secondvariable resistance layer 106 b 2, it is possible to increase the filmthickness of the second variable resistance layer 106 b andsignificantly reduce leak currents, and thus voltage can be morereliably applied to the cell and further lowering of the break voltagebecomes possible. Therefore, lowering the break voltage and suppressingvariation therein can both be achieved, and miniaturization andincreased capacity of memories can be realized.

It should be noted that, in the present embodiment, the verticalplacement of the first variable resistance layer 106 a and the secondvariable resistance layer 106 b may be reversed. Furthermore, pluralsteps may be formed in the surface of the first variable resistancelayer 106 a.

Embodiment 7

When a memory array is configured by two-dimensionally arranging memorycells each of which having the nonvolatile memory device described inthe above-described Embodiments 1 to 6, there are cases where resistancechange is caused only in a predetermined memory cell (selected memorycell) and resistance change is prevented in the rest of the memory cells(non-selected memory cells). In such a case, each of the memory cellsare configured by connecting a diode element in series to the variableresistance element, and it is sufficient to turn ON the diode element ofthe predetermined memory cell and turn OFF the respective diode elementsof the rest of the memory cells. In this case, it is necessary to add avoltage portion to be distributed to the diode element, and thus raisethe voltage to be applied to the memory cell. As such, the demand forlowering voltage is even greater.

In the nonvolatile memory device in the present embodiment, it ispossible to lower the break voltage of the variable resistance element,and thus the voltage applied to the memory cell can be lowered.Furthermore, in the structures of the respective embodiments describedearlier, the break phenomenon of the variable resistance element occurslocally, and thus transient current flowing at the time of the break canbe reduced. With this, destruction of the diode element can also beprevented.

These shall be described in detail below.

[Device Configuration]

FIG. 21( a) is a cross-sectional view of a nonvolatile memory device 44in Embodiment 7 of the present invention, and (b) is a plan view of thefirst variable resistance layer 106 a included therein. In FIG. 21, thesame numerical references are used for elements that are the same as inFIG. 1, and description thereof shall not be repeated.

As shown in FIGS. 21( a) and (b), the difference between the nonvolatilememory device 44 in Embodiment 7 and the nonvolatile memory device 10 inEmbodiment 1 is that a lower electrode 112 of a diode element, asemiconductor layer 113, and an upper electrode 114 of the diodeelement, that is, a diode element is built-in below the variableresistance element. In other words, in the nonvolatile memory device 44,the element is formed by integrating the variable resistance element andthe diode element.

Although the nonvolatile memory device 44 has a structure in which theupper electrode 114 of the diode element and the bottom electrode 105 ofthe variable resistance element are shared, these electrodes may beconfigured separately. Here, the surface of the lower electrode 112 ofthe diode element is planarized, and the surface of the element film ofthe semiconductor layer 113 formed above it is formed to beapproximately flat. Furthermore, as in the nonvolatile memory device 10,the straight step 106 ax is formed in the surface of the first variableresistance layer 106 a.

According to this configuration, although the lower electrode 112 of thediode element is also formed in the part of the recess created above thefirst contact plug 104 inside the first contact hole 103, the surface ofthe lower electrode 112 of the diode element is formed flat. Since thesemiconductor layer 113 can be formed on a planarized base, variation inthe film thickness thereof can be greatly reduced, and it is possible toobtain stable rectifying characteristics of an MSM diode in which thesemiconductor layer 113 is held between upper and lower electrodes.Meanwhile, in the variable resistance element, the bend 106 bx of thesecond variable resistance layer 106 b is formed above the step 106 axof the first variable resistance layer 106 a, and thus it is possible,through electric field concentration, to cause the initial breakphenomenon even with a low voltage, with the bend 106 bx as a startingpoint of the initial break. Furthermore, since the step shape of thefirst variable resistance layer 106 a is formed in an intentional andcontrolled manner, the shape of the bend 106 bx of the second variableresistance layer 106 b is stable, and thus variation in break voltagedoes not increase.

With such a memory cell structure in which the variable resistanceelement and the diode element are connected in series, the break voltageof the variable resistance element can be lowered, and thus the voltageapplied to the memory cell can be lowered. Furthermore, since the breakphenomenon of the variable resistance element occurs locally, transientcurrent flowing at the time of the break can be reduced. With this,destruction of the diode element can also be prevented.

[Manufacturing Method]

FIG. 22( a) to (i) are cross-sectional views showing a method ofmanufacturing main parts of the nonvolatile memory device 44 inEmbodiment 7 of the present invention. The method of manufacturing themain parts of the nonvolatile memory device 44 shall be described usingthis figure. Furthermore, processes prior to FIG. 22( a) are the same asshown in FIG. 2( a) to (e), and thus description thereof shall not berepeated.

As shown in FIG. 22( a), in a process of forming a conductive layer 112′(the lower electrode 112) of the diode element, the conductive layer112′ (film thickness: 50 to 200 nm) comprising a tantalum nitride andwhich later becomes the lower electrode 112 of the diode element isformed with the sputtering method, on the first interlayer insulatinglayer 102 and covering the first contact plug 104. The conductive layer112′ is also formed in the part of the recess created above the firstcontact plug 104 inside the first contact hole 103. Furthermore, adepression reflecting the shape of the base is created in the top planeof the conductive layer 105′ on the first contact plug 104.

Next, as shown in FIG. 22( b), in a process of forming the lowerelectrode 112 of the diode element, planarization polishing using thechemical mechanical polishing method (CMP method) is performed on theentire surface of the wafer to form the conductive layer 112″ (filmthickness: 20 to 100 nm) which becomes the lower electrode 112 of thediode element after patterning. The point of this process is to performplanarization polishing on the conductive layer 112′ until theabove-described depression created in FIG. 22( a) disappears, and toleave behind the entire conductive layer 112″. According to such amanufacturing method, the step created on the first contact plug 4 isnot transferred onto the surface of the conductive layer 112″, and thusthe lower electrode 112 is extremely flat throughout the entire surface,and a continuous plane can be maintained. This is because, unlike whenthe contact plug 104 is formed, what is polished is always the same typeof material because the polishing of the conductive layer 112″ isstopped along the way, and thus, in principle, the difference inpolishing rates in the CMP method can be avoided.

Next, as shown in FIG. 22( c), in a process of forming a semiconductorlayer 113′ of the diode element, the semiconductor layer 113′ isdeposited on the conductive layer 112″. The semiconductor layer 113′ isformed by depositing, for example, 5 to 30 nm of silicon nitride usingthe sputtering method.

Next, as shown in FIG. 22( d), in a process of forming a conductivelayer 114′ (the upper electrode 114) of the diode element, theconductive layer 114′ which becomes the upper electrode of the diodeelement is deposited on the semiconductor layer 113′. The conductivelayer 114′ which becomes the upper electrode 114 of the diode element isformed by depositing, for example, 20 to 50 nm of tantalum nitride usingthe sputtering method. The upper electrode 114 of the diode element alsoserves as the lower electrode 105 of the variable resistance element.

As shown in FIG. 22( e), in the process of forming the first variableresistance layer 106 a′, the first variable resistance layer 106 a′comprising a transitional metal oxide is formed on the conductive layer114′ (the conductive layer 105′). Here, the first variable resistancelayer 106 a′ is formed using what is called a reactive sputtering methodin which sputtering is performed on a tantalum target in an argon (Ar)and oxygen gas atmosphere. The oxygen content of the first variableresistance layer 106 a′ is 50 to 65 atm %, the resistivity is 2 to 50mΩcm, and the film thickness is 20 to 100 nm.

Next, as shown in FIG. 22( f), in the process of forming the step 106 axin the first variable resistance layer 106 a′, the straight step 106 ax(height: 1 to 30 nm) is formed, using the desired mask, in the surfaceof the first variable resistance layer 106 a′ and extending to anadjacent variable resistance element. On this occasion, it is preferablethat an inert gas such as Ar be used as the etching gas in order toprevent fluorine (F), and so on, included in the etching gas fromentering the first variable resistance layer 106 a′ and causing etchingdamage which causes the film property of the variable resistance layerto deteriorate. Furthermore, it is also preferable to perform wetetching using an etching liquid containing hydrofluoric acid (HF) and soon. In this case, the fluorine (F) included in the etching liquid doesnot enter the variable resistance layer, and thus the variableresistance layer does not deteriorate.

As shown in FIG. 22( g), in the process of forming the second variableresistance layer 106 b′, the second variable resistance layer 106 b′having a higher oxygen content than the first variable resistance layer106 a′ is formed on the first variable resistance layer 106 a′. In thesame manner as in the first variable resistance layer 106 a′, the secondvariable resistance layer 106 b′ is formed with the reactive sputteringmethod of performing sputtering on a tantalum target in an oxygen gasatmosphere. The oxygen content of the second variable resistance layer106 b′ is 67 to 71 atm %, the resistivity is 10⁷ mΩcm or greater, andthe film thickness is 2 to 10 nm. The bend 106 bx of the second variableresistance layer 106 b′ is formed above the step 106 ax in the surfaceof the first variable resistance layer 106 a′. Here, the film thicknessof the bend 106 bx (the film thickness on the side wall of the step 106ax) of the second variable resistance layer 106 b′ can be adjusted to bethin according to the height of the step 106 ax base, and a thin-filmpart can be formed locally in a stable manner. Furthermore, compared tothe flat part of the second variable resistance layer 106 b′, the filmproperty tends to become sparse in the bend 106 bx of the secondvariable resistance layer 106 b′, and thus a film that allows easybreaking can be realized. Although the variable resistance layer isformed using reactive sputtering, a reactive sputtering method ofperforming sputtering on a tantalum oxide target in an oxygen gasatmosphere may be used, and the variable resistance layer may be formedby plasma oxidation in an atmosphere that includes oxygen.

Next, as shown in FIG. 22( h), in the process of forming the conductivelayer 107′ (the upper electrode 107), the conductive layer 107′comprising a noble metal (platinum, iridium, palladium, and so on) whichbecomes the upper electrode 107 after patterning is formed on the secondvariable resistance layer 106 b′.

Lastly, as shown in FIG. 22( i), in the process of forming the variableresistance element and the diode element, patterning using the desiredmask is performed on the conductive layer 112″, the semiconductor layer113′, the conductive layer 114′, the first variable resistance layer 106a′, the second variable resistance layer 106 b′, and the conductivelayer 107′ to integrally form (i) the diode element in which thesemiconductor layer 113 is held between electrodes and (ii) the variableresistance element in which the variable resistance layer 106 configuredof stacked layers is held between electrodes. Although, in the presentprocess, patterning is performed collectively using the same mask,patterning may be performed on a per process basis (a per differentlayer basis). In addition, the second interlayer insulating layer 108(film thickness: 500 to 1000 nm) is formed covering the variableresistance element and the diode element, and the second contact hole109 and the second contact plug 110 are formed according to the samemanufacturing method as shown in FIGS. 2( b) and (c). Subsequently, thesecond line 111 is formed covering the second contact plug 110, and thenonvolatile memory device 44 is completed.

By adopting the above-described manufacturing method, it is possible torealize, in a memory cell structure in which the variable resistanceelement and the diode element are connected in series, an element whichallows the break voltage of the variable resistance element to belowered. Since the break voltage of the variable resistance element canbe lowered, it is possible to reduce the voltage applied to the entirecell. Furthermore, since the break phenomenon of the variable resistanceelement occurs locally in the bend 106 bx, transient current flowing atthe time of the break can be reduced. With this, destruction of thediode element can also be prevented.

It should be noted that although the present embodiment describes anexample in which the diode element is placed below the first variableresistance layer 106 a in the configuration in Embodiment 7 (FIG. 21),the same operation and effect as in Embodiment 7 can be produced evenwith a configuration (modification) in which a lower electrode 127, thesemiconductor layer 113, and an upper electrode 128 are placed above thefirst variable resistance layer 106 a in the configuration in Embodiment3 (FIG. 9), as shown in FIG. 23. In this case, it is preferable toperform, on the upper electrode 107, the chemical mechanical polishingmethod (CMP method) to eliminate the transferring of the step 105 s ofthe variable resistance layer 106.

Furthermore, although the step 106 ax is straight-shaped in the presentembodiment, the step 106 ax may have the ring shape described inEmbodiment 2, Embodiment 4, and embodiment 5. Furthermore, plural stepsmay be formed in the surface of the first variable resistance layer 106a. The above described details may also be applied in the same manner inthe modification shown in FIG. 23 mentioned above.

Moreover, as described in Embodiment 6, the ring-shaped step 106 ax maybe formed after forming the stacked layers of the first variableresistance layer 106 a and the second variable resistance layer 106 b′(the second variable resistance layer 106 b 1). The second variableresistance layer 106 b may be formed by additionally stacking the secondvariable resistance layer 106 b′ (106 b 2) to cover the step 106 ax.

Modifications of Embodiments 1 to 7

Although, in the respective embodiments described above, the metal oxidelayer is configured of a stacked structure of tantalum oxide layers, theabove described operation and effect of the present invention aremanifested not only in the case of tantalum oxide layers, and thus thepresent invention is not limited to the above configuration. Forexample, the metal oxide layer may be configured of a different metaloxide layer (transitional metal oxide layer) such as a stacked structureof hafnium (Hf) oxide layers or a stacked structure of zirconium (Zr)oxide layers.

For example, in the case of adopting a stacked structure of hafniumoxide layers, when the composition of a first hafnium oxide layer isHfO_(x) and the composition of a second hafnium oxide layer is HfO_(y),it is preferable that x approximately satisfies 0.9≦x≦1.6 and yapproximately satisfies 1.8<y<2.0, and that the film thickness of thesecond hafnium oxide layer be between 3 nm and 4 nm, inclusive.

Furthermore, in the case of adopting a stacked structure of zirconiumoxide layers, when the composition of a first zirconium oxide layer isZrO_(x) and the composition of a second zirconium oxide layer isZrO_(y), it is preferable that x approximately satisfies 0.9≦x≦1.4 and yapproximately satisfies 1.9<y<2.0, and that the film thickness of thesecond zirconium oxide layer be between 1 nm and 5 nm, inclusive.

Furthermore, in the case of adopting hafnium oxide layers, the firsthafnium oxide layer is formed on the lower electrode with what is calledthe reactive sputtering method in which sputtering is performed in anargon gas and oxygen gas atmosphere using a Hf target. The secondhafnium oxide layer can be formed after the forming of the first hafniumoxide layer, by exposing the surface of the first hafnium oxide layer toargon gas and oxygen gas plasma. The oxygen content of the first hafniumoxide layer is the same as in the case of the above-described tantalumoxide layer, and can be easily adjusted by changing the flow ratio ofthe oxygen gas to the argon gas in the reactive sputtering. It should benoted that, with regard to the substrate temperature, heating is notnecessary and room temperature is acceptable.

Furthermore, the film thickness of the second hafnium oxide layer can beeasily adjusted through the exposure time to the argon gas and oxygengas plasma. When the composition of the first hafnium oxide layer isHfO_(x) and the composition of the second hafnium oxide layer isHfO_(y), it is possible to realize stable resistance changecharacteristics when 0.9≦x≦1.6 and 1.8<y<2.0, and the film thickness ofthe second hafnium oxide layer is within a range of 3 nm to 4 nm,inclusive.

In the case of adopting zirconium oxide layers, the first zirconiumoxide layer is formed on the lower electrode with what is called thereactive sputtering method in which sputtering is performed in an argongas and oxygen gas atmosphere using a Zr target. The second zirconiumoxide layer can be formed after the forming of the first zirconium oxidelayer, by exposing the surface of the first zirconium oxide layer toargon gas and oxygen gas plasma. The oxygen content of the firstzirconium oxide layer is the same as in the case of the above-describedtantalum oxide layer, and can be easily adjusted by changing the flowratio of the oxygen gas to the argon gas in the reactive sputtering. Itshould be noted that, with regard to the substrate temperature, heatingis not necessary and room temperature is acceptable.

Furthermore, the film thickness of the second zirconium oxide layer canbe easily adjusted through the exposure time to the argon gas and oxygengas plasma. When the composition of the first zirconium oxide layer isZrO_(x) and the composition of the second hafnium oxide layer isZrO_(y), it is possible to realize stable resistance changecharacteristics when 0.9≦x≦1.4 and 1.9<y<2.0, and the film thickness ofthe second zirconium oxide layer is within a range of 1 nm to 5 nm,inclusive.

Furthermore, the respective materials of the upper electrode and thelower electrode described in Embodiments 1 to 7 are examples, and othermaterials may be used. For example, aside from Pt, Ir, and Pd, gold(Au), copper (Cu), silver (Ag), and so on, may be used as an upperelectrode, and, aside from TaN, tungsten (W), nickel (Ni), and so on,may be used as a lower electrode.

Furthermore, providing a bend in the second variable resistance layer inEmbodiments 1 to 7 includes the case where the step in the interfacebetween the first variable resistance layer and the second variableresistance layer is transferred onto a position in the surface of thesecond variable resistance layer that corresponds to such step.Furthermore, in the second variable resistance layer, the film thicknessin the bend may be thinner than in the other parts of the secondvariable resistance layer, or may be the same as in the other parts.

INDUSTRIAL APPLICABILITY

The present invention provides a variable resistance nonvolatile memorydevice and a method of manufacturing the same, and is useful in variouselectronic device fields that use a nonvolatile memory because thepresent invention can realize a nonvolatile memory which operates in astable manner and is highly reliable.

REFERENCE SIGNS LIST

10, 20, 30, 40, 41, 42, 43, 44, 50, 60 Nonvolatile memory device

100 Substrate

101 First line

102 First interlayer insulating layer

103 First contact hole

104 First contact plug

104′, 105′, 105″, 107′, 112′, 112″, 114′ Conductive layer

105, 112, 127 Lower electrode

105 s, 105 t, 106 ax, 106 ay, 106 ax 1, 106 ax 2, 106 az Step

106 Variable resistance layer

106 a, 106 a′ First variable resistance layer (low oxygen content layer,low resistance layer)

106 b, 106 b′ 106 b 1, 106 b 2 Second variable resistance layer (highoxygen content layer, high resistance layer)

106 bx, 106 by, 106 bs, 106 bt Bend

107, 114, 128 Upper electrode

108 Second interlayer insulating layer

109 Second contact hole

110 Second contact plug

111 Second line

113, 113′ Semiconductor layer

1-11. (canceled)
 12. A nonvolatile memory device comprising: asubstrate; a lower electrode formed above said substrate; a firstvariable resistance layer formed above said lower electrode andcomprising a first transitional metal oxide; a second variableresistance layer formed above said first variable resistance layer andcomprising a second transitional metal oxide having an oxygen contentthat is higher than an oxygen content of the first transitional metaloxide; and an upper electrode formed above said second variableresistance layer, wherein a step is formed in an interface between saidfirst variable resistance layer and said second variable resistancelayer, and said second variable resistance layer is formed covering thestep and has a bend above the step.
 13. A nonvolatile memory devicecomprising: a substrate; a lower electrode formed above said substrate;a second variable resistance layer formed above said lower electrode andcomprising a second transitional metal oxide; a first variableresistance layer formed above said second variable resistance layer andcomprising a first transitional metal oxide having an oxygen contentthat is lower than an oxygen content of the second transitional metaloxide; and an upper electrode formed above said first variableresistance layer, wherein a step is formed in an interface between saidlower electrode and said second variable resistance layer, and saidsecond variable resistance layer is formed covering the step and has abend above the step.
 14. The nonvolatile memory device according toclaim 12, further comprising a contact plug below said lower electrode,wherein an interface between said lower electrode and said firstvariable resistance layer is flat.
 15. The nonvolatile memory deviceaccording to claim 12, wherein the bend of said second variableresistance layer is straight-shaped when said second variable resistancelayer is seen from above.
 16. The nonvolatile memory device according toclaim 12, wherein the bend of said second variable resistance layer isring-shaped when said second variable resistance layer is seen fromabove.
 17. The nonvolatile memory device according to claim 12, whereinthe step includes plural steps, and there is a crossing point at whichthe plural steps cross each other.
 18. The nonvolatile memory deviceaccording to claim 12, wherein the first transitional metal oxide andthe second transitional metal oxide each comprise an oxide of tantalum,hafnium, or zirconium.
 19. The nonvolatile memory device according toclaim 12, wherein a diode element is formed in contact with said lowerelectrode or said upper electrode.
 20. The nonvolatile memory deviceaccording to claim 13, wherein the bend of said second variableresistance layer is straight-shaped when said second variable resistancelayer is seen from above.
 21. The nonvolatile memory device according toclaim 13, wherein the bend of said second variable resistance layer isring-shaped when said second variable resistance layer is seen fromabove.
 22. The nonvolatile memory device according to claim 13, whereinthe step includes plural steps, and there is a crossing point at whichthe plural steps cross each other.
 23. The nonvolatile memory deviceaccording to claim 13, wherein the first transitional metal oxide andthe second transitional metal oxide each comprise an oxide of tantalum,hafnium, or zirconium.
 24. The nonvolatile memory device according toclaim 13, wherein a diode element is formed in contact with said lowerelectrode or said upper electrode.
 25. A method of manufacturing anonvolatile memory device, said method comprising: forming a lowerelectrode above a substrate; forming a first variable resistance layerabove the lower electrode, the first variable resistance layercomprising a first transitional metal oxide; forming a step in a surfaceof the first variable resistance layer; forming a second variableresistance layer to cover the step of the first variable resistancelayer and have a bend above the step, the second variable resistancelayer comprising a second transitional metal oxide having an oxygencontent that is higher than an oxygen content of the first transitionalmetal oxide; and forming an upper electrode above the second variableresistance layer.
 26. A method of manufacturing a nonvolatile memorydevice, said method comprising: forming a lower electrode above asubstrate; forming a step in a surface of the lower electrode; forming asecond variable resistance layer to cover the step of the lowerelectrode and have a bend above the step, the second variable resistancelayer comprising a second transitional metal oxide; forming a firstvariable resistance layer above the second variable resistance layer,the first variable resistance layer comprising a first transitionalmetal oxide having an oxygen content that is lower than an oxygencontent of the second transitional metal oxide; and forming an upperelectrode above the first variable resistance layer.
 27. A method ofmanufacturing a nonvolatile memory device, said method comprising:forming a lower electrode above a substrate; forming a first variableresistance layer above the lower electrode, the first variableresistance layer comprising a first transitional metal oxide; forming asecond variable resistance layer above the first variable resistancelayer, the second variable resistance layer comprising a secondtransitional metal oxide having an oxygen content that is higher than anoxygen content of the first transitional metal oxide; additionallystacking the second variable resistance layer after forming a step inthe second variable resistance layer, so as to cover the step; andforming an upper electrode above the additionally-stacked secondvariable resistance layer.